KR102257063B1 - Light-emitting element, light-emitting device, electronic device, and lighting device - Google Patents

Abstract

It provides a new light emitting device. It provides a light emitting device with a long life. A light-emitting device having high luminous efficiency is provided. It provides a new organic compound. A novel organic compound having hole transport properties is provided. Provides a new hole transport material. It provides a hole transport material comprising an organic compound having a substituted or unsubstituted benzonaphthofuran skeleton and a substituted or unsubstituted amine skeleton. It provides a light emitting device using the hole transport material. It provides an organic compound in which an amine skeleton containing two aromatic hydrocarbon groups having 6 to 60 carbon atoms is bonded to the 6 position or 8 position of the benzonaphthofuran skeleton.

Description

A light-emitting element, a light-emitting device, an electronic device, and a lighting device {LIGHT-EMITTING ELEMENT, LIGHT-EMITTING DEVICE, ELECTRONIC DEVICE, AND LIGHTING DEVICE}

One embodiment of the present invention relates to a light-emitting element, a display module, a lighting module, a display device, a light-emitting device, an electronic device, and a lighting device. In addition, one embodiment of the present invention is not limited to the above-described technical field. The technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. In addition, one aspect of the present invention relates to a process, a machine, a manufacture, or a composition of matter. Specifically, examples of the technical field of one embodiment of the present invention disclosed in the present specification include a semiconductor device, a display device, a liquid crystal display device, a light emitting device, a lighting device, a power storage device, a memory device, an imaging device, and a driving method of any of them, And a manufacturing method of any of these.

A light-emitting element (organic EL element) containing an organic compound and using electroluminescence (EL) has been put into practical use. In the basic structure of such a light-emitting element, an organic compound layer (EL layer) containing a light-emitting material is provided between a pair of electrodes. By applying a voltage to this device, carriers are injected, and by using the recombination energy of the carriers, light emission can be obtained from the light-emitting material.

Since the light-emitting element is a self-luminous element, when it is used as a pixel of a display, it has advantages such as high visibility and no need for a backlight, and is suitable as a flat panel display element. In addition, there is a great advantage that a display including such a light emitting device can be manufactured as a thin and light display. In addition, its characteristic feature is that the response speed is very fast.

In such a light-emitting element, since the light-emitting layer can be continuously formed in two dimensions, surface light emission can be obtained. This feature is difficult to realize by a point light source represented by an incandescent lamp and an LED, or a line light source represented by a fluorescent lamp. Therefore, the light-emitting element has high utility value as a surface light source applied to a lighting device or the like.

As described above, a display or lighting device including a light emitting device may be suitably used for various electronic devices, and research and development of a light emitting device are being conducted for higher efficiency or longer life.

The organic compound having acceptor properties is a material for a hole injection layer used to facilitate injection of carriers, particularly holes, into the EL layer. Organic compounds having acceptor properties can be easily deposited by evaporation, so they are suitable for mass production and are widely used. However, if the LUMO level of the organic compound having an acceptor property is separated from the HOMO level of the organic compound contained in the hole transport layer, it is difficult to inject holes into the EL layer. On the other hand, when the HOMO level of the organic compound included in the hole transport layer is raised to be close to the LUMO level of the organic compound having acceptor properties, the difference between the HOMO level of the emission layer and the HOMO level of the organic compound included in the hole transport layer is large. , Even when holes can be injected into the EL layer, it becomes difficult to inject holes from the hole transport layer into the host material of the light emitting layer.

In the configuration disclosed in Patent Document 1, a hole transport material in which the HOMO level is between the HOMO level of the first hole injection layer and the HOMO level of the host material is provided between the light emitting layer and the first hole transport layer in contact with the hole injection layer. have.

Although the characteristics of the light-emitting device have been remarkably improved, high demands for various characteristics including efficiency and durability have not yet been satisfied.

International Publication No. WO2011/065136

From the above-described viewpoint, it is an object of one embodiment of the present invention to provide a novel light-emitting device. It is another object of one embodiment of the present invention to provide a light emitting device having a long life. Another object of one embodiment of the present invention is to provide a light emitting device having high luminous efficiency. It is another object of one embodiment of the present invention to provide a novel organic compound. It is another object of one embodiment of the present invention to provide a novel organic compound having hole transport properties. It is another object of one embodiment of the present invention to provide a novel hole transport material.

Another object of one embodiment of the present invention is to provide a highly reliable light emitting device, electronic device, and display device. Another object of one embodiment of the present invention is to provide a light-emitting device, an electronic device, and a display device with low power consumption.

In the present invention, it is sufficient that at least one of the above-described problems can be achieved.

One embodiment of the present invention is a hole transport material comprising an organic compound having a substituted or unsubstituted benzonaphthofuran skeleton and a substituted or unsubstituted amine skeleton.

Another aspect of the present invention is a hole transport material comprising an organic compound having a substituted or unsubstituted benzonaphthofuran skeleton and one substituted or unsubstituted amine skeleton.

Another aspect of the present invention is a hole transport material having any of the above-described configurations, wherein the amine skeleton is bonded to the 6 position or 8 position of the benzonaphthofuran skeleton.

Another aspect of the present invention is a hole transport material having any of the above-described configurations in which the benzonaphthofuran skeleton is directly bonded to the nitrogen atom of the amine skeleton.

Another embodiment of the present invention is a light-emitting element comprising an anode, a cathode, and an EL layer. The EL layer includes a light emitting layer and is positioned between the anode and the cathode. The EL layer contains the hole transport material according to any one of the above.

Another embodiment of the present invention is a light-emitting element comprising an anode, a cathode, and an EL layer. The EL layer is located between the anode and the cathode, and includes a light emitting layer and a hole transport layer. The hole transport layer is positioned between the light emitting layer and the anode, and includes a hole transport material according to any one of the above.

Another aspect of the present invention is a light-emitting element having any of the above-described configurations, wherein the light-emitting layer includes a light-emitting material and the hole transport material.

Another aspect of the present invention is a light-emitting element having any of the above-described configurations, wherein the light-emitting layer further includes an electron transport material.

Another aspect of the present invention is an organic compound represented by general formula (G1).

[Formula 1]

In addition, in the general formula (G1), R ¹ to R ⁸ are independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogenated group. It represents any one of a lozene, a C1-C6 haloalkyl group, and a substituted or unsubstituted C6-C60 aromatic hydrocarbon group. One of A and B represents a group represented by the general formula (g1), and the other is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, halogen, and 1 to 6 carbon atoms. Represents a haloalkyl group, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms.

[Formula 2]

Further, in the general formula (g1), Ar ¹ and Ar ² independently represent either a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms and a group represented by the general formula (g2). When Ar ¹ and Ar ² are each an aromatic hydrocarbon group having 6 to 60 carbon atoms and include a substituent, the substituent includes a benzonaphthofuranyl group and a dynapthofuranyl group.

[Formula 3]

In addition, in the general formula (g2), R ¹¹ to R ¹⁸ are independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogenated group. It represents any one of a lozene, a C1-C6 haloalkyl group, and a substituted or unsubstituted C6-C60 aromatic hydrocarbon group. One of Z ¹ and Z ² is bonded to a nitrogen atom in the general formula (g1), and the other is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a halogen, and a carbon number. Represents any one of a haloalkyl group having 1 to 6, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms.

Another aspect of the present invention is an organic compound having any of the above-described configurations, wherein the group represented by the general formula (g1) is a group represented by the general formula (g3).

[Formula 4]

In addition, in the general formula (g3), Ar ³ and Ar ⁴ are independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, a substituted or unsubstituted benzonaphthofuranyl group, and a substituted or unsubstituted diner. Represents any one of the ptofuranyl groups. Ar ⁵ and Ar ⁶ independently represent a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 54 carbon atoms, and n and m independently represent 0 to 2. In addition, ^{the sum of the carbon number of Ar 3} and Ar ⁵ is 60 or less, and the sum of the carbon number of Ar ⁴ and Ar ⁶ is 60 or less.

In another embodiment of the present invention, Ar ³ and Ar ⁴ are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, and a substituted or unsubstituted pyrenyl group. It is an organic compound having any of the above-described configurations showing one.

In another embodiment of the present invention, Ar ⁵ and Ar ⁶ are independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, and a substituted or unsubstituted pyrene. It is an organic compound which has any one of the above-described configurations representing any one of the yylene groups.

Another aspect of the present invention is an organic compound having any of the above-described configurations ^{, wherein Ar 3} and Ar ^{4 are each a phenyl group.}

Another aspect of the present invention is an organic compound having any of the above-described configurations ^{, wherein Ar 5} and Ar ^{6 are each a phenylene group.}

Another aspect of the present invention is an organic compound having any of the above-described configurations, wherein one of n and m is 1 and the other is 0.

Another embodiment of the present invention is a light-emitting element comprising an anode, a cathode, and an EL layer. The EL layer is located between the anode and the cathode. The EL layer contains an organic compound having any of the above-described configurations.

Another embodiment of the present invention is a light-emitting element comprising an anode, a cathode, and an EL layer. The EL layer is located between the anode and the cathode, and includes a light emitting layer. The light-emitting layer includes an organic compound having any of the above-described configurations.

Another aspect of the present invention is a light-emitting element having any of the above-described configurations, wherein the light-emitting layer further includes a light-emitting material.

Another aspect of the present invention is a light-emitting element having any of the above-described configurations, wherein the light-emitting layer further includes a material having electron transport properties.

Another embodiment of the present invention is a light-emitting element comprising an anode, a cathode, and an EL layer. The EL layer is located between the anode and the cathode. The EL layer includes a light emitting layer and a hole transport layer. The hole transport layer is located between the emission layer and the anode. The hole transport layer contains an organic compound having any of the above-described configurations.

In another aspect of the present invention, the EL layer further includes a hole injection layer, the hole injection layer is in contact with the anode and the hole transport layer, and the hole injection layer includes an organic compound having an acceptor property. It is a light-emitting element having any of the above-described configurations.

Another aspect of the present invention is that the organic compound having the acceptor property is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene. Phosphorus, a light-emitting device having any of the above-described configurations.

In another aspect of the present invention, the hole transport layer includes a first layer, a second layer, and a third layer, the first layer is located between the hole injection layer and the second layer, and the third A layer is positioned between the second layer and the light-emitting layer, the first layer is in contact with the hole injection layer, the third layer is in contact with the light-emitting layer, and the first layer contains a first hole transport material, , The second layer includes the organic compound, the third layer includes a third hole transport material, the emission layer includes a host material and a light-emitting material, and the HOMO level of the organic compound is the first hole The above-described configuration, wherein the HOMO level of the transport material is deeper, the HOMO level of the host material is deeper than the HOMO level of the organic compound, and the difference between the HOMO level of the organic compound and the HOMO level of the third hole transport material is 0.3 eV or less. It is a light-emitting device having any of.

Another aspect of the present invention is a light emitting device having any of the above-described configurations, wherein the HOMO level of the first hole transport material is -5.4 eV or more.

Another aspect of the present invention is a light emitting device having any of the above-described configurations, wherein the difference between the HOMO level of the first hole transport material and the HOMO level of the organic compound is 0.3 eV or less.

Another aspect of the present invention is a light emitting device having any of the above-described configurations, wherein the difference between the HOMO level of the organic compound and the HOMO level of the third hole transport material is 0.2 eV or less.

Another aspect of the present invention is a light emitting device having any of the above-described configurations, wherein the difference between the HOMO level of the first hole transport material and the HOMO level of the organic compound is 0.2 eV or less.

Another aspect of the present invention is a light-emitting device having any of the above-described configurations, wherein the HOMO level of the light-emitting material is higher than the HOMO level of the host material.

Another aspect of the present invention is a light emitting device having any of the above-described configurations, wherein the HOMO level of the third hole transport material is greater than or equal to the HOMO level of the host material.

Another aspect of the present invention is a light-emitting device having any of the above-described configurations, wherein the light-emitting material is a fluorescent material.

Another aspect of the present invention is a light-emitting device having any of the above-described configurations, in which the light-emitting material emits blue fluorescence.

Another aspect of the present invention is a light-emitting device having any of the above-described configurations, wherein the light-emitting material is a condensed aromatic diamine compound.

Another aspect of the present invention is a light-emitting device having any of the above-described configurations, wherein the light-emitting material is a diaminopyrene compound.

Another embodiment of the present invention is a light-emitting device including a light-emitting element having any of the above-described configurations, and a transistor or a substrate.

Still another aspect of the present invention is an electronic device including the above-described light emitting device and a sensor, an operation button, a speaker, or a microphone.

Another aspect of the present invention is a lighting device including the above-described light emitting device and a housing.

Further, the light-emitting device in the present specification includes an image display device using a light-emitting element. A light-emitting device includes a module in which a connector such as an anisotropic conductive film or a TCP (tape carrier package) is provided to the light-emitting element, a module provided with a printed wiring board at the end of the TCP, and an integrated circuit (IC) by a chip on glass (COG) method. Directly mounted modules may be included. Further, the light emitting device may be included in a lighting fixture or the like.

According to one embodiment of the present invention, a novel light emitting device can be provided. A light emitting device having a long life can be provided. A light-emitting device having high luminous efficiency can be provided. New organic compounds can be provided. A novel organic compound having hole transport properties can be provided. A new hole transport material can be provided.

According to still another aspect of the present invention, a light emitting device, an electronic device, and a display device with high reliability can be provided. A light emitting device, an electronic device, and a display device having low power consumption can be provided.

In addition, the description of these effects does not interfere with the existence of other effects. One embodiment of the present invention does not necessarily have to achieve all of the above-described effects. Other effects will become apparent and can be extracted from the description of the specification, drawings, and claims.

1A to 1C are schematic diagrams of a light emitting element.
2A and 2B are conceptual diagrams of an active matrix light emitting device.
3A and 3B are conceptual diagrams of an active matrix light emitting device.
4 is a conceptual diagram of an active matrix light emitting device.
5A and 5B are conceptual diagrams of a passive matrix light emitting device.
6A and 6B show a lighting device.
7A to 7D show electronic devices.
8 shows a light source device.
9 shows a lighting device.
10 shows a lighting device.
11 illustrates a vehicle-mounted display device and a lighting device.
12A to 12C show electronic devices.
13A to 13C show electronic devices.
14A and 14B show ¹ H NMR charts of BnfABP.
15 shows an absorption spectrum and an emission spectrum of a solution of BnfABP.
16 shows an absorption spectrum and an emission spectrum of a thin film of BnfABP.
Figure 17 (A) and (B) shows the ¹ H NMR chart of BBABnf.
18 shows the absorption spectrum and emission spectrum of the solution of BBABnf.
19 shows an absorption spectrum and an emission spectrum of a thin film of BBABnf.
20 shows the luminance-current density characteristics of Light-Emitting Element 1.
21 shows current efficiency-luminance characteristics of Light-Emitting Element 1.
22 shows the luminance-voltage characteristics of Light-Emitting Element 1.
23 shows current-voltage characteristics of Light-Emitting Element 1.
24 shows external quantum efficiency-luminance characteristics of Light-Emitting Element 1.
25 shows an emission spectrum of Light-Emitting Element 1.
26 shows the time dependence of the normalized luminance of Light-Emitting Element 1.
27 shows the luminance-current density characteristics of Light-Emitting Elements 2 and 3;
28 shows current efficiency-luminance characteristics of Light-Emitting Elements 2 and 3;
29 shows the luminance-voltage characteristics of Light-Emitting Elements 2 and 3;
30 shows current-voltage characteristics of Light-Emitting Elements 2 and 3;
31 shows external quantum efficiency-luminance characteristics of Light-Emitting Elements 2 and 3;
32 shows emission spectra of Light-Emitting Elements 2 and 3.
33 shows the time dependence of the normalized luminance of Light-Emitting Elements 2 and 3;
34A to 34D are cross-sectional views showing a method of manufacturing an EL layer.
35 is a conceptual diagram showing a droplet discharge device.
(A) and (B) of Figure 36 shows the ¹ H NMR chart of BBABnf (6).
37 shows the absorption spectrum and emission spectrum of the solution of BBABnf(6).
38 shows the absorption spectrum and emission spectrum of the thin film of BBABnf(6).
Figure 39 (A) and (B) shows the ¹ H NMR chart of BBABnf (8).
40 shows the absorption spectrum and emission spectrum of the solution of BBABnf(8).
41 shows the absorption spectrum and emission spectrum of the thin film of BBABnf(8).
42 shows the luminance-current density characteristics of Light-Emitting Elements 4 and 5.
43 shows current efficiency-luminance characteristics of Light-Emitting Elements 4 and 5.
44 shows luminance-voltage characteristics of Light-Emitting Elements 4 and 5.
45 shows current-voltage characteristics of Light-Emitting Elements 4 and 5.
46 shows external quantum efficiency-luminance characteristics of Light-Emitting Elements 4 and 5.
47 shows emission spectra of Light-Emitting Elements 4 and 5.
48 shows the time dependence of the normalized luminance of Light-Emitting Elements 4 and 5.
49 shows the luminance-current density characteristics of Light-Emitting Elements 6 and 7.
50 shows current efficiency-luminance characteristics of Light-Emitting Elements 6 and 7.
51 shows the luminance-voltage characteristics of Light-Emitting Elements 6 and 7.
52 shows current-voltage characteristics of Light-Emitting Elements 6 and 7.
53 shows external quantum efficiency-luminance characteristics of Light-Emitting Elements 6 and 7.
54 shows emission spectra of Light-Emitting Elements 6 and 7.
55 shows the luminance-current density characteristics of Light-Emitting Element 8.
56 shows current efficiency-luminance characteristics of Light-Emitting Element 8.
57 shows the luminance-voltage characteristics of Light-Emitting Element 8.
58 shows current-voltage characteristics of Light-Emitting Element 8.
59 shows external quantum efficiency-luminance characteristics of Light-Emitting Element 8.
60 shows an emission spectrum of Light-Emitting Element 8.
61 shows the time dependence of the normalized luminance of Light-Emitting Element 8.

An embodiment of the present invention will be described in detail below with reference to the drawings. In addition, it is easily understood by those skilled in the art that the present invention is not limited to the following description, and that the form and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be interpreted as being limited to the contents of the following embodiments.

(Embodiment 1)

The lifespan of a light-emitting device including an organic material may be particularly affected by the characteristics of the hole transport material. First of all, the transportability of the hole transport material greatly affects the lifespan, and the lifespan greatly varies depending on the type of the hole transport material.

The present inventors believe that a hole transport material comprising an organic compound having a substituted or unsubstituted benzonaphthofuran skeleton and a substituted or unsubstituted amine skeleton has suitable transport properties, and the lifespan of a light emitting device including the hole transport material is improved. It was found that it contributes to elevating.

In particular, it is preferable that the hole transport material includes an organic compound having a substituted or unsubstituted benzonaphthofuran skeleton and one substituted or unsubstituted amine skeleton. More preferably, if the benzonaphthofuran skeleton of the organic compound of the hole transport material is a benzo[ b ]naphtho[1,2- d ]furan skeleton, a highly reliable device can be provided. More preferably, the hole transport material contains an organic compound in which the amine skeleton is bonded to the 6 position or 8 position of the benzo[b ]naphtho[1,2- d]furan skeleton.

If the hole transport material contains an organic compound in which the nitrogen atom of the amine skeleton is directly bonded to the benzonaphthofuran skeleton without a substituent, a highly reliable light emitting device can be provided, and the HOMO level of the hole transport material is suitable. The hole transporting material including an organic compound in which the nitrogen atom of the amine skeleton is directly bonded to the benzonaphthofuran skeleton without a substituent is preferable because it can provide a light emitting device having a low driving voltage because of high hole transportability.

A light-emitting element using a hole transport material for the EL layer can have a longer life.

1A to 1C show a light emitting device of one embodiment of the present invention. The light emitting device of one embodiment of the present invention includes an anode 101, a cathode 102, and an EL layer 103 using a hole transport material containing the above-described organic compound, respectively.

The EL layer 103 may include a light emitting layer 113 and may also include a hole transport layer 112. The light-emitting layer 113 includes a light-emitting material and a host material, and light is emitted from the light-emitting material of the light-emitting element of one embodiment of the present invention. The hole transport material of one embodiment of the present invention may be contained in one or both of the light emitting layer 113 and the hole transport layer 112.

1A to 1C further illustrate the hole injection layer 111, the electron transport layer 114, and the electron injection layer 115, but the configuration of the light emitting device is not limited thereto. .

The hole transport material can also be used as a host material. Further, the hole transport material and the electron transport material may be deposited by co-deposition so that an excited composite is formed of the electron transport material and the hole transport material. Efficient energy transfer to a light-emitting material is possible by an excited composite having an appropriate light-emitting wavelength, and it becomes possible to realize a light-emitting element with high efficiency and a long lifespan.

Since the above-described hole transport material exhibits good hole transport properties, it is suitable for the hole transport layer 112. In particular, when the hole transport material includes an organic compound having an acceptor property in which the hole injection layer 111 is provided between the hole transport layer 112 and the anode 101 and facilitates injection of holes from the electrode It is preferable to use.

When hole injection is performed using an organic compound having an acceptor property, the compound included in the hole transport layer 112 in contact with the hole injection layer 111 prevents the extraction of electrons by the organic compound having the acceptor property. For ease of use, it is preferred that the HOMO level is a relatively shallow hole transport material. However, holes cannot be easily injected from a hole transport material having a relatively shallow HOMO level to the light emitting layer 113, and the light emitting layer 113 is formed to contact the hole transport layer 112 made of a hole transport material having a relatively shallow HOMO level. In this case, carriers accumulate at the interface, and the life and efficiency of the light-emitting element are reduced. Therefore, if a layer containing an organic compound of one embodiment of the present invention is provided between the light emitting layer 113 and a hole transport material having a relatively shallow HOMO level, holes can be easily injected into the light emitting layer, and the lifespan of the light emitting device and Efficiency can be improved.

That is, the hole transport layer 112 includes a first hole transport layer 112-1 and a second hole transport layer 112-2 from the hole injection layer 111 side, and the first hole transport layer 112-1 is Although one hole transport material is included, the second hole transport layer 112-2 contains one type of hole transport material of the present invention. Since the HOMO level of the hole transport material of one embodiment of the present invention is deeper than the HOMO level of the first hole transport material, a light emitting device having a long life and high efficiency is realized. Further, if the HOMO level of the first hole transport material is -5.4 eV or more, it is preferable because electrons can be easily extracted from the organic compound having an acceptor property.

Preferably, the difference between the HOMO level of the first hole transport material and the HOMO level of the hole transport material of the present invention is 0.3 eV or less, more preferably 0.2 eV or less, and in this case, the hole is the first hole transport layer 112-1 ) Can be easily injected into the second hole transport layer 112-2.

The hole transport layer 112 may further include a third hole transport layer 112-3 between the second hole transport layer 112-2 and the light emitting layer, and the third hole transport layer 112-3 is a third hole transport material. You may include. In this case, the HOMO level of the third hole transport material is preferably deeper than the HOMO level of the hole transport material of one embodiment of the present invention contained in the second hole transport layer 112-2, and the difference between the HOMO levels is preferably Is 0.3 eV or less, more preferably 0.2 eV or less.

The HOMO level of the third hole transport material is preferably deeper or equal to the HOMO level of the host material, and in this case, holes are suitably transported to the light emitting layer, thereby increasing the life and efficiency.

In addition, when the HOMO level of the light-emitting material is shallower (higher) than the HOMO level of the host material, the ratio of holes injected into the light-emitting material increases according to the position of the HOMO level of the hole transport layer, and holes are trapped in the light-emitting material, The lifespan may be reduced due to the non-uniformly located light emitting area. In this case, it is preferable to apply the configuration of the light emitting device of the present invention to, for example, a blue fluorescent device. In particular, the configuration of the present invention can be preferably used for an aromatic diamine compound emitting excellent blue fluorescence, more specifically a pyrendiamine compound, and the like, and thus a light emitting device having excellent lifespan, efficiency, and chromaticity can be realized.

Next, examples of the specific structure and material of the above-described light emitting device will be described. As described above, the light emitting device of one embodiment of the present invention includes an EL layer 103 positioned between a pair of electrodes (anode 101 and cathode 102) and having a plurality of layers. In the EL layer 103, at least a hole injection layer 111, a hole transport layer 112, and a light emitting layer 113 are provided from the anode 101 side.

There is no particular limitation on other layers included in the EL layer 103, and various layers such as a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a carrier blocking layer, an exciton blocking layer, and a charge generation layer can be employed. I can.

The anode 101 is preferably formed using any of a metal having a high work function (specifically, a work function of 4.0 eV or more), an alloy, a conductive compound, and a mixture thereof. Specific examples include indium tin oxide (ITO), indium oxide containing silicon or silicon oxide-tin oxide, indium oxide-zinc oxide, and indium oxide (IWZO) containing tungsten oxide and zinc oxide. This includes. Such a conductive metal oxide film is generally formed by a sputtering method, but may be formed by applying a sol-gel method or the like. In an example of the formation method, indium oxide-zinc oxide is deposited by a sputtering method using a target obtained by adding 1 wt% to 20 wt% of zinc oxide to indium oxide. In addition, a film of indium oxide (IWZO) containing tungsten oxide and zinc oxide was formed by a sputtering method using a target to which 0.5 wt% to 5 wt% of tungsten oxide and 0.1 wt% to 1 wt% of zinc oxide were added to indium oxide. Can be formed. Alternatively, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), or a nitride of a metal material (eg, titanium nitride), or the like can be used. You can also use graphene. Further, if the composite material described later is used for the layer in the EL layer 103 in contact with the anode 101, the electrode material can be selected irrespective of the work function.

In addition to the hole injection layer 111, the hole transport layer 112, and the light emitting layer 113, the configuration shown in FIG. 1(A) including an electron transport layer 114 and an electron injection layer 115, and a hole injection layer (111), a hole transport layer 112, and in addition to the light emitting layer 113, the configuration shown in FIG. 1(B) including an electron transport layer 114, an electron injection layer 115, and a charge generation layer 116 The lamination structure of the two types of EL layers 103 will be described. The material forming each layer will be described in detail below.

The hole injection layer 111 includes a material having an acceptor property. It is preferable that the constitution of one embodiment of the present invention is used when an organic compound having an acceptor property is used. As an organic compound having an acceptor property, a compound containing an electron withdrawing group (halogen group or cyano group), for example, 7,7,8,8-tetracyano-2,3,5,6-tetra Fluoroquinodimethane (abbreviation: F4-TCNQ), 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane, chloranyl, or 2,3, 6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN) can be used. The organic compound having an acceptor property is preferable because a compound in which an electron withdrawing group is bonded to a condensed aromatic ring having a plurality of hetero atoms, such as HAT-CN, is thermally stable. An organic compound having acceptor properties can extract electrons from an adjacent hole transport layer (or hole transport material) by applying an electric field.

When an organic compound having an acceptor property is not used for the hole injection layer 111, molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, or manganese oxide may be used as a material having an acceptor property. . Alternatively, phthalocyanine compounds such as phthalocyanine (abbreviation: H ₂ Pc) or copper phthalocyanine (CuPc), 4,4'-bis[ N- (4-diphenylaminophenyl) -N -Phenylamino]biphenyl (abbreviation: DPAB) or N , N' -bis{4-[bis(3-methylphenyl)amino]phenyl} -N , N' -diphenyl-(1,1'-biphenyl) Aromatic amine compounds such as -4,4'-diamine (abbreviation: DNTPD), or polymer compounds such as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS) are used Thus, the hole injection layer 111 may be formed.

Alternatively, for the hole injection layer 111, a composite material in which a material having hole transport properties includes an acceptor material may be used. By using a composite material in which the material having the hole transport property includes an acceptor material, the material used to form the electrode can be selected regardless of the work function. In other words, in addition to a material having a high work function, a material having a low work function can also be used for the anode 101. Examples of acceptor substances include 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranyl, or 1,3 Organic compounds having acceptor properties such as ,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCNNQ), and transition metal oxides are included. Alternatively, oxides of metals belonging to groups 4 to 8 of the periodic table may be used. When using vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, or rhenium oxide as an oxide of a metal belonging to groups 4 to 8 of the periodic table, These are preferable because of their high electron acceptability. Among them, molybdenum oxide is particularly preferable because it is stable in the air, has low hygroscopicity, and is easy to handle.

As the material having hole transport properties for use in the composite material, any of various organic compounds such as aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, and high molecular compounds (eg, oligomers, dendrimers, or polymers) can be used. In addition, the material having hole transport properties used in the composite material ^{is preferably a material having a hole mobility of 10 -6} cm ² /Vs or more. Organic compounds that can be used as a material having hole transport properties in a composite material are specifically shown below.

Examples of aromatic amine compounds that can be used in composite materials include N , N' -di( p -tolyl) -N , N' -diphenyl- p -phenylenediamine (abbreviation: DTDPPA), 4,4'- Bis[ N- (4-diphenylaminophenyl) -N -phenylamino]biphenyl (abbreviation: DPAB), N , N' -bis{4-[bis(3-methylphenyl)amino]phenyl} -N , N ' -Diphenyl-(1,1'-biphenyl)-4,4'-diamine (abbreviation: DNTPD), and 1,3,5-tris[ N -(4-diphenylaminophenyl)- N- Phenylamino]benzene (abbreviation: DPA3B) is included. Specific examples of carbazole derivatives include 3-[ N- (9-phenylcarbazol-3-yl) -N -phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[ N- (9-phenylcarbazol-3-yl) -N -phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), 3-[ N -(1-naphthyl)- N -(9-phenylcarbazole- 3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1), 4,4'-di( N -carbazolyl)biphenyl (abbreviation: CBP), 1,3,5-tris[4-( N -carbazolyl) phenyl] benzene (abbreviation: TCPB), 9- [4- ( 10- phenyl-anthracene-9-yl) phenyl] -9 H-carbazole (abbreviation: CzPA), and 1,4-bis [4 -( N -carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene. Examples of aromatic hydrocarbons include 2- tert -butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 2- tert -butyl-9,10-di(1-naphthyl)anthracene , 9,10-bis (3,5-diphenylphenyl) anthracene (abbreviation: DPPA), 2- tert -butyl-9,10-bis (4-phenylphenyl) anthracene (abbreviation: t-BuDBA), 9, 10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10-diphenylanthracene (abbreviation: DPAnth), 2- tert -butylanthracene (abbreviation: t-BuAnth), 9,10-bis(4) -Methyl-1-naphthyl)anthracene (abbreviation: DMNA), 2- tert -butyl-9,10-bis[2-(1-naphthyl)phenyl]anthracene, 9,10-bis[2-(1- Naphthyl)phenyl]anthracene, 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, 2,3,6,7-tetramethyl-9,10-di(2- Naphthyl) anthracene, 9,9'-bianthryl, 10,10'-diphenyl-9,9'-biathryl, 10,10'-bis(2-phenylphenyl)-9,9'-bi Anthryl, 10,10'-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-biathryl, anthracene, tetracene, rubrene, perylene, and 2, 5,8,11-tetra( tert -butyl)perylene. In addition, pentacene or coronene may be used. The aromatic hydrocarbon may have a vinyl skeleton. Examples of the aromatic hydrocarbon having a vinyl group include 4,4'-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi) and 9,10-bis[4-(2,2-diphenylvinyl)phenyl ]There is anthracene (abbreviation: DPVPA). In addition, an organic compound of one embodiment of the present invention can also be used. In this case, it is preferable to use F6-TCNNQ as the acceptor material.

Poly( N -vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[ N -(4-{ N '-[4-(4-diphenylamino) Phenyl]phenyl- N' -phenylamino}phenyl)methacrylamide] (abbreviation: PTPDMA), or poly[ N , N' -bis(4-butylphenyl) -N , N' -bis(phenyl)benzidine]( Abbreviation: poly-TPD) can also be used.

By providing the hole injection layer, it is possible to realize high hole injection properties and drive the light emitting device at a low voltage.

Further, the hole injection layer may be formed alone or in combination with the above-described acceptor material. In this case, the acceptor material extracts electrons from the hole transport layer, so that holes can be injected into the hole transport layer. The acceptor material transports the extracted electrons to the anode.

By providing the hole injection layer 111, it is possible to realize high hole injection properties and drive the light emitting device at a low voltage. In addition, an organic compound having an acceptor property is easily deposited by vapor deposition, so it is easy to use.

The hole transport layer 112 includes a hole transport material. It is preferable that the hole transport material has a hole mobility of 1×10 ^-6 cm ^{2 /Vs or more.} If the hole transport layer 112 includes the hole transport material of one embodiment of the present invention, a light emitting device having a long life and high efficiency can be provided, and thus it is preferable.

In particular, when an organic compound having an acceptor property is used for the hole injection layer 111, at least the hole injection layer 111 is composed of two layers of the first and second hole transport layers, and the HOMO level is relatively shallow. When the first hole transport material is used for the first hole injection layer and the hole transport material of one embodiment of the present invention is used for the second hole transport layer, a light emitting device having a long life and high efficiency can be provided.

The difference between the LUMO level of the organic compound having the acceptor property and the HOMO level of the first hole transport material is not particularly limited because it depends on the strength of the acceptor property of the organic compound having the acceptor property, but the difference between the levels is about 1 eV. If it is below, holes can be injected. Since the LUMO level of HAT-CN is estimated to be -4.41 eV by cyclic voltammetry measurement, when HAT-CN is used as an organic compound having an acceptor property, the HOMO level of the first hole transport material is -5.4 eV. It is preferable that it is above. In addition, if the HOMO level of the first hole transport material is too high, the hole injection property to the second hole transport material deteriorates. Further, since the work function of an anode such as ITO is about -5 eV, it is disadvantageous when a material having a HOMO level higher than -5 eV is used as the first hole transport material. Therefore, it is preferable that the HOMO level of the first hole transport material is -5.0 eV or less.

A third hole transport layer may be formed between the second hole transport layer and the light emitting layer. The third hole transport layer contains a third hole transport material.

The first to third hole transport layers have been described above and will not be described repeatedly. Further, the hole transport material included in each hole transport layer can be selected from the above-described material having hole transport property or other various materials having hole transport property so that the layers have an appropriate relationship.

The light-emitting layer 113 includes a host material and a light-emitting material. As the light-emitting material, a fluorescent material, a phosphorescent material, a material exhibiting thermally activated delayed fluorescence (TADF), or another light-emitting material may be used. Further, the light-emitting layer 113 may be a single layer or may include a plurality of layers containing different light-emitting materials. Further, one embodiment of the present invention is more preferably used when the light emitting layer 113 emits fluorescence, specifically, blue fluorescence.

An example of a material that can be used as a fluorescent material in the light emitting layer 113 will be described below. It is also possible to use fluorescent materials other than those shown below.

Examples of fluorescent substances include 5,6-bis[4-(10-phenyl-9-anthryl)phenyl]-2,2'-bipyridine (abbreviation: PAP2BPy), 5,6-bis[4'-( 10-phenyl-9-anthryl)biphenyl-4-yl]-2,2'-bipyridine (abbreviation: PAPP2BPy), N , N' -diphenyl- N , N' -bis[4-(9- phenyl -9 H - fluoren-9-yl) phenyl] pyrene-1,6-diamine (abbreviation: 1,6FLPAPrn), N, N ' - bis (3-methylphenyl) - N, N' - bis [3 - (9-phenyl -9 H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (abbreviation: 1,6mMemFLPAPrn), N, N ' - bis [4- (9 H-carbazole 9-yl) phenyl] - N, N '- diphenyl-stilbene-4,4'-diamine (abbreviation: YGA2S), 4- (9 H-carbazole-9-yl) -4' - (10 -phenyl-9-anthryl) triphenyl amine (abbreviation: YGAPA), 4- (9 H-carbazole-9-yl) -4 '- (9,10-diphenyl-2-anthryl) triphenyl amine (abbreviation: 2YGAPPA), N, 9- diphenyl - N - [4- (10- phenyl-9-anthryl) phenyl] -9 H - carbazol-3-amine (abbreviation: PCAPA), perylene, 2 ,5,8,11-tetra- tert -butylperylene (abbreviation: TBP), 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9 H -carbazol-3-yl ) Triphenylamine (abbreviation: PCBAPA), N , N'' -(2- tert -butylanthracene-9,10-diyldi-4,1-phenylene)bis[ N , N ', N' -tri phenyl-1,4-phenylenediamine (abbreviation: DPABPA), N, 9- diphenyl - N - [4- (9,10- diphenyl-2-anthryl) phenyl] -9 H - carbazol -3-amine (abbreviation: 2PCAPPA), N- [4-(9,10-diphenyl-2-anthryl)phenyl] -N , N ', N' -triphenyl-1,4-phenylenediamine (Abbreviation: 2DPAPPA), N , N , N' , N' , N'' , N'' , N''' , N''' - octaphenyldibenzo[g , p ]Chrisene-2,7, 10,15-tetraamine (abbreviation: DBC1), coumarin 30, N- (9,10-diphenyl-2-anthryl) -N ,9-diphenyl-9 H -Carbazol-3-amine (abbreviation: 2PCAPA), N - [9,10- bis (1,1'-biphenyl-2-yl) -2-anthryl] - N, 9- diphenyl -9 H -Carbazole-3-amine (abbreviation: 2PCABPhA), N- (9,10-diphenyl-2-anthryl) -N , N' , N' -Triphenyl-1,4-phenylenediamine (abbreviation : 2DPAPA), N -[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]- N , N' , N' -triphenyl-1,4-phenylenedia Min (abbreviation: 2DPABPhA), 9,10-bis(1,1'-biphenyl-2-yl)- N -[4-(9 H -carbazol-9-yl)phenyl] -N -phenylanthracene- 2-amine (abbreviation: 2YGABPhA), N , N , 9-triphenylanthracene-9-amine (abbreviation: DPhAPhA), coumarin 545T, N , N' -diphenylquinacridone (abbreviation: DPQd), rubrene, 5,12-bis(1,1'-biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT), 2-(2-{2-[4-(dimethylamino)phenyl) ]Ethenyl}-6-methyl-4 H -pyran-4-ylidene) propaneinitril (abbreviation: DCM1), 2-{2-methyl-6-[2-(2,3,6,7) -tetrahydro -1 H, 5 H - benzo [ij] quinolinium Jean-9-yl) ethenyl] -4 H-pyran-4-ylidene} propane die nitrile (abbreviation: DCM2), N, N , N' , N' -tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl- N , N , N' , N' -tetrakis (4-methylphenyl)acenaphtho[1,2- a ]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD), 2-{2-isopropyl-6-[2-(1,1) ,7,7-tetramethyl-2,3,6,7-tetrahydro-1 H ,5 H -benzo[ ij ]quinolizin-9-yl)ethenyl]-4 H -pyran-4-ylidene }Propainyneitril (abbreviation: DCJTI), 2-{2- tert -butyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1 H, 5 H - benzo [ij] quinolinium binary ethenyl on-9-yl)] -4 H - pyran-4-ylidene} propane die nitrile (abbreviation: DCJTB) , 2-(2,6-bis{2-[4-(dimethylamino)phenyl]ethenyl}-4 H -pyran-4-ylidene) propanenaitryl (abbreviation: BisDCM), 2-{ 2,6-bis[2-(8-methoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1 H ,5 H -benzo[ ij ]quinolizine- 9- yl) ethenyl] -4 H-pyran-4-ylidene} propane die nitrile (abbreviation: BisDCJTM), and N, N '- diphenyl - N, N' - (1,6- propylene- Diyl)bis[(6-phenylbenzo[ b ]naphtho[1,2- d ]furan)-8-amine] (abbreviation: 1,6BnfAPrn-03). Condensed aromatic diamine compounds typified by pyrendiamine compounds such as 1,6FLPAPrn, 1,6mMemFLPAPrn, and 1,6BnfAPrn-03 are particularly preferred because of their high hole trapping properties, high luminous efficiency, and high reliability.

Examples of materials that can be used as a phosphorescent material in the light emitting layer 113 are as follows.

In the above example, tris {2-[5-(2-methylphenyl)-4-(2,6-dimethylphenyl)-4 H -1,2,4-triazol-3-yl-κ N 2]phenyl-κ C }Iridium (III) (abbreviation: [Ir (mpptz-dmp) ₃ ]), tris (5-methyl-3,4-diphenyl-4 H -1,2,4-triazolato) iridium (III) (Abbreviation: [Ir(Mptz) ₃ ]), and tris[4-(3-biphenyl)-5-isopropyl-3-phenyl- 4H -1,2,4-triazolato]iridium(III) Organometallic iridium complexes having a 4H -triazole skeleton such as (abbreviation: [Ir(iPrptz-3b) _{3 ]);} Tris[3-methyl-1-(2-methylphenyl)-5-phenyl-1 H -1,2,4-triazolato]iridium(III) (abbreviation: [Ir(Mptz1-mp) ₃ ]) and tris (1-methyl-5-phenyl-3-propyl -1 H -1,2,4- triazol reyito) iridium (III) (abbreviation: [Ir (-Prptz1 Me) _3]), 1 H, such as-triazole Organometallic iridium complex having a skeleton; fac -tris[(1-2,6-diisopropylphenyl)-2-phenyl-1 H -imidazole]iridium(III) (abbreviation: [Ir(iPrpmi) ₃ ]) and tris[3-(2, Organics having an imidazole skeleton such as 6-dimethylphenyl)-7-methylimidazo[1,2- f ]phenanthridineto]iridium(III) (abbreviation: [Ir(dmpimpt-Me) _{3 ])} Metal iridium complex; And bis[2-(4',6'-difluorophenyl )pyridinato-N , C ^2' ]iridium(III)tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2 -(4',6'-difluorophenyl)pyridinato- N , C ^2' ]iridium(III)picolinate (abbreviation: FIrpic), bis {2-[3',5'-bis( Trifluoromethyl)phenyl]pyridinato- N , C ^2' }iridium(III)picolinate (abbreviation: [Ir(CF ₃ ppy) ₂ (pic)]), and bis[2-(4',6'-difluorophenyl )pyridinato-N , C ^2' ]Iridium(III)acetylacetonate (abbreviation: FIracac), and other organometallic iridium complexes in which a phenylpyridine derivative having an electron withdrawing group is a ligand. do. These are compounds that emit blue phosphorescence and have an emission peak at 440 nm to 520 nm.

Other examples include tris(4-methyl-6-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(mppm) ₃ ]), tris(4- t -butyl-6-phenylpyrimidinato)iridium (III) (abbreviation: [Ir (tBuppm) ₃ ]), (acetylacetonato) bis (6-methyl-4-phenylpyrimidinato) iridium (III) (abbreviation: [Ir (mppm) ₂ (acac )]), (acetylacetonato)bis(6- tert -butyl-4-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(tBuppm) ₂ (acac)]), (acetylacetonato )Bis[6-(2-norbornyl)-4-phenylpyrimidinato]iridium(III) (abbreviation: [Ir(nbppm) ₂ (acac)]), (acetylacetonato)bis[5-methyl -6-(2-methylphenyl)-4-phenylpyrimidinato]iridium(III) (abbreviation: [Ir(mpmppm) ₂ (acac)]), and (acetylacetonato)bis(4,6-di Organometallic iridium complexes having a pyrimidine skeleton such as phenylpyrimidineto) iridium (III) (abbreviation: [Ir(dppm) _{2 (acac)]);} (Acetylacetonato)bis(3,5-dimethyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-Me) ₂ (acac)]) and (acetylacetonato)bis Organometallic iridium complexes having a pyrazine skeleton such as (5-isopropyl-3-methyl-2-phenylpyrazinato) iridium (III) (abbreviation: [Ir(mppr-iPr) _{2 (acac)]);} Tris (2-phenylpyridinato- N , C ^2' ) iridium (III) (abbreviation: [Ir(ppy) ₃ ]), bis (2-phenylpyridinato- N , C ^2' ) iridium ( III) Acetylacetonate (abbreviation: [Ir(ppy) ₂ (acac)]), bis(benzo[ h ]quinolinato)iridium(III)acetylacetonate (abbreviation: [Ir(bzq) ₂ (acac)) ]), tris(benzo[ h ]quinolinato)iridium(III) (abbreviation: [Ir(bzq) ₃ ]), tris(2- phenylquinolinato-N , C ^2' )iridium(III) (Abbreviation: [Ir(pq) ₃ ]), and bis(2-phenylquinolinato- N , C ^2′ ) iridium (III) acetylacetonate (abbreviation: [Ir(pq) ₂ (acac)]) Organometallic iridium complexes having a pyridine skeleton, such as; And rare earth metal complexes such as tris (acetylacetonato) (monophenanthroline) terbium (III) (abbreviation: [Tb(acac) _{3 (Phen)]).} These are mainly compounds that emit green phosphorescence and have an emission peak between 500 nm and 600 nm. In addition, an organometallic iridium complex having a pyrimidine skeleton is particularly preferred because of its remarkably high reliability and luminous efficiency.

In another example, (diisobutylylmethanato)bis[4,6-bis(3-methylphenyl)pyrimidinato]iridium(III) (abbreviation: [Ir(5mdppm) ₂ (dibm)]), bis [4,6-bis(3-methylphenyl)pyrimidinato](dipivaloylmethanato)iridium(III) (abbreviation: [Ir(5mdppm) ₂ (dpm)]), bis[4,6- Organometallic iridium having a pyrimidine skeleton such as di(naphthalen-1-yl)pyrimidinato](dipivaloylmethanato)iridium(III) (abbreviation: [Ir(d1npm) _{2 (dpm)])} Complex; (Acetylacetonato)bis(2,3,5-triphenylpyrazinato)iridium(III) (abbreviation: [Ir(tppr) ₂ (acac)]), bis(2,3,5-triphenylpyra Ginato)(dipivaloylmethanato)iridium(III) (abbreviation: [Ir(tppr) ₂ (dpm)]), and (acetylacetonato)bis[2,3-bis(4-fluoro Organometallic iridium complexes having a pyrazine skeleton such as phenyl)quinoxalinato]iridium(III) (abbreviation: [Ir(Fdpq) _{2 (acac)]);} Tris(1-phenylisoquinolinato- N , C ^2' ) Iridium(III) (abbreviation: [Ir(piq) ₃ ]) and bis(1-phenylisoquinolinato- N , C ^2' ) Organometallic iridium complexes having a pyridine skeleton such as iridium(III)acetylacetonate (abbreviation: [Ir(piq) _{2 (acac)]);} 2,3,7,8,12,13,17,18-octaethyl -21 H, 23 H - porphyrin platinum (II): a platinum complex such as (abbreviation; PtOEP); And tris(1,3-diphenyl-1,3-propanedioneto)(monophenanthroline) europium(III) (abbreviation: [Eu(DBM) ₃ (Phen)]) and tris[1-( Includes rare earth metal complexes such as 2-tenoyl)-3,3,3-trifluoroacetonato] (monophenanthroline) europium (III) (abbreviation: [Eu(TTA) _{3 (Phen)]))} do. These are compounds that emit red phosphorescence and have an emission peak at 600 nm to 700 nm. In addition, the organometallic iridium complex having a pyrazine skeleton can provide red light emission with good chromaticity.

In addition to the above-described phosphorescent compound, a known phosphorescent material may be selected and used.

Examples of TADF materials include fullerene, derivatives thereof, acridine, derivatives thereof, eosin derivatives, and magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In ), or a metal-containing porphyrin such as porphyrin including palladium (Pd). Examples of metal-containing porphyrins include protoporphyrin-tin fluoride complex (SnF ₂ (Proto IX)), mesoporphyrin-tin fluoride complex (SnF ₂ (Meso IX)), and hematoporphyrin- Tin fluoride complex (SnF ₂ (Hemato IX)), coproporphyrin tetramethyl ester-tin fluoride complex (SnF ₂ (Copro III-4Me)), octaethyl porphyrin-tin fluoride complex (SnF ₂ (OEP)) , An ethioporphyrin-tin fluoride complex (SnF ₂ (Etio I)), and an octaethylporphyrin-platinum chloride complex (PtCl ₂ (OEP)).

[Formula 5]

Or 2-(biphenyl-4-yl)-4,6-bis(12-phenylindolo[2,3- a ]carbazol-11-yl)-1,3,5 represented by the following structural formula -Triazine (abbreviation: PIC-TRZ), 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9'-phenyl-9 H ,9' H -3,3 "- By carbazole (abbreviation: PCCzTzn), 9- [4- ( 4,6- diphenyl-1,3,5-triazine-2-yl) phenyl] phenyl -9'- -9 H, 9 ' H -3,3'-bicarbazole (abbreviation: PCCzPTzn), 2-[4-(10 H -phenoxazin-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (Abbreviation: PXZ-TRZ), 3-[4-(5-phenyl-5,10-dihydrophenazine-10-yl)phenyl]-4,5-diphenyl-1,2,4-triazole ( Abbreviation: PPZ-3TPT), 3-(9,9-dimethyl-9 H -acridin-10-yl)-9 H -xanthene-9-one (abbreviation: ACRXTN), bis[4-(9 , 9-dimethyl-9,10-dihydro-acridine) phenyl] sulfone (abbreviation: DMAC-DPS), or 10-phenyl -10 H, 10 'H - spy [acridine -9,9'-Anthracene]-10'-one (abbreviation: ACRSA), etc., and a heterocyclic compound having both of a π electron-excessive heteroaromatic ring and a π electron-deficient heteroaromatic ring can be used. Since the heterocyclic compound has a π electron-excessive heteroaromatic ring and a π-electron deficient heteroaromatic ring, it is preferable because of its high electron transport property and hole transport property. In addition, the substance in which the π electron-excessive heteroaromatic ring is directly bonded to the π electron-deficient heteroaromatic ring increases both the donor property of the π electron-excessive heteroaromatic ring and the acceptor property of the π electron-deficient heteroaromatic ring. , Since _{the energy difference between the S 1} level and the T ₁ level is small, thermally activated delayed fluorescence can be obtained with high efficiency, which is particularly preferable. Further, instead of the π electron deficient heteroaromatic ring, an aromatic ring to which an electron withdrawing group such as a cyano group is bonded may be used.

[Formula 6]

As the host material of the light emitting layer, various carrier transport materials, such as a material having electron transport properties and a material having hole transport properties, can be used.

The following is an example of a material having a hole-transporting: 4,4'-bis [N - (1- naphthyl) - N - phenylamino] biphenyl (abbreviation: NPB), N, N ' - bis (3-methylphenyl ) -N , N' -diphenyl-[1,1'-biphenyl]-4,4'-diamine (abbreviation: TPD), 4,4'-bis[ N -(spiro-9,9' -Bifluoren-2-yl) -N -phenylamino]biphenyl (abbreviation: BSPB), 4-phenyl-4'-(9-phenylfluoren-9-yl) triphenylamine (abbreviation: BPAFLP), 4-phenyl-3 '- (9-phenyl-fluoren-9-yl) triphenyl amine (abbreviated: mBPAFLP), 4-phenyl-4' - (9-phenyl -9 H-carbazole-3-yl) tri Phenylamine (abbreviation: PCBA1BP), 4,4'-diphenyl-4''-(9-phenyl-9 H -carbazol-3-yl) triphenylamine (abbreviation: PCBBi1BP), 4-(1-naph) Tyl)-4'-(9-phenyl-9 H -carbazol-3-yl)triphenylamine (abbreviation: PCBANB), 4,4'-di(1-naphthyl)-4''-(9- Phenyl-9 H -carbazol-3-yl) triphenylamine (abbreviation: PCBNBB), 9,9-dimethyl- N -phenyl- N -[4-(9-phenyl-9 H -carbazole-3- Yl)phenyl]fluoren-2-amine (abbreviation: PCBAF), and N -phenyl- N- [4-(9-phenyl-9 H -carbazol-3-yl)phenyl]spiro-9,9' -Compounds having an aromatic amine skeleton such as bifluoren-2-amine (abbreviation: PCBASF); 1,3-bis( N -carbazolyl)benzene (abbreviation: mCP), 4,4'-di( N -carbazolyl)biphenyl (abbreviation: CBP), 3,6-bis(3,5-diphenyl) phenyl) -9-phenyl-carbazole (abbreviation: CzTP), and 3,3'-bis (9-phenyl -9 H - carbazole) (abbreviation: PCCP) a compound having a carbazole skeleton and the like; 4,4',4''-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II), 2,8-diphenyl-4-[4-(9 -phenyl -9 H-fluoren-9-yl) phenyl] dibenzo thiophene (abbreviation: DBTFLP-III), and 4- [4- (9-phenyl -9 H-fluoren-9-yl) phenyl] Compounds having a thiophene skeleton such as -6-phenyldibenzothiophene (abbreviation: DBTFLP-IV), and 4,4',4''-(benzene-1,3,5-triyl)tri(dibenzo Furan) (abbreviation: DBF3P-II) and 4-{3-[3-(9-phenyl-9 H -fluoren-9-yl) phenyl] phenyl} dibenzofuran (abbreviation: mmDBFFLBi-II), etc. Compounds with a skeleton. Among the materials described above, compounds having an aromatic amine skeleton and a compound having a carbazole skeleton are preferable because they have high reliability, high hole transport properties, and contribute to a reduction in driving voltage.

The following are examples of materials having electron transport properties: bis(10-hydroxybenzo[ h ]quinolinato)beryllium(II) (abbreviation: BeBq ₂ ), bis(2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III) (abbreviation: BAlq), bis (8-quinolinolato) zinc (II) (abbreviation: Znq), bis[2- (2-benzoxazolyl) phenolato] Metal complexes such as zinc(II) (abbreviation: ZnPBO), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ); 2-(4-biphenylyl)-5-(4- tert -butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 3-(4-biphenylyl)-4-phenyl- 5-(4- tert -butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 1,3-bis[5-( p - tert -butylphenyl)-1,3,4-oxadia 2-yl] benzene (abbreviation: OXD-7), 9- [ 4- (5- phenyl-1,3,4-oxadiazol-2-yl) phenyl] -9 H - carbazole (abbreviation: CO11), 2,2',2''-(1,3,5-benzenetriyl)tris(1-phenyl- 1H -benzimidazole) (abbreviation: TPBI), and 2-[3-(di Heterocyclic compounds having a polyazole skeleton such as benzothiophen-4-yl)phenyl]-1-phenyl-1 H -benzimidazole (abbreviation: mDBTBIm-II); 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[ f , h ]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3'-(dibenzothiophen-4-yl) biphenyl-3-yl] dibenzo [f, h] quinoxaline (abbreviation: 2mDBTBPDBq-II), 2- [ 3 '- (9 h - carbazol-9-yl) biphenyl-3-yl] dibenzo [ f , h ]quinoxaline (abbreviation: 2mCzBPDBq), 4,6-bis[3-(phenanthren-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), and 4,6-bis[3- Heterocyclic compounds having a diazine skeleton such as (4-dibenzothienyl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II); And 3,5-bis [4- (9 H - carbazol-9-yl) phenyl] pyridine (abbreviation: 35DCzPPy) and 1,3,5-tri [3- (3-pyridyl) phenyl] benzene (abbreviation; : Heterocyclic compounds having a pyridine skeleton such as TmPyPB). Among the materials described above, a heterocyclic compound having a diazine skeleton and a heterocyclic compound having a pyridine skeleton are preferable because of their high reliability. In particular, a heterocyclic compound having a diazine (pyrimidine or pyrazine) skeleton has high electron transport properties and contributes to a reduction in driving voltage.

When a fluorescent material is used as the light emitting material, it is preferable to use a material having an anthracene skeleton as the host material. When a material having an anthracene skeleton is used as a host material for a fluorescent material, a light emitting layer having high luminous efficiency and high durability can be obtained. Since most of the materials having an anthracene skeleton have a deep HOMO level, such a material can be preferably used in one embodiment of the present invention. As the substance having an anthracene skeleton, a substance having a diphenylanthracene skeleton, in particular, a substance having a 9,10-diphenylanthracene skeleton, is chemically stable, and thus is preferably used as a host material. If the host material has a carbazole skeleton, it is preferable because the hole injection property and hole transport property are increased, and if the host material has a benzocarbazole skeleton in which a benzene ring is more condensed in the carbazole, the HOMO level is about 0.1 eV shallower than carbazole. It is more preferable because the hole easily enters the host material because of the loss. Particularly, when the host material contains a dibenzocarbazole skeleton, the HOMO level is about 0.1 eV higher than that of carbazole, so that holes are easily introduced into the host material, hole transport properties are improved, and heat resistance is increased, which is preferable. Therefore, as the host material, a substance having both a 9,10-diphenylanthracene skeleton and a carbazole skeleton (or benzocarbazole or dibenzocarbazole skeleton) is more preferable. Further, from the viewpoints of the above-described hole injection properties and hole transport properties, a benzofluorene skeleton or a dibenzofluorene skeleton may be used instead of the carbazole skeleton. Examples of such substances include 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9 H -carbazole (abbreviation: PCzPA), 3-[4-(1-naphthyl) -Phenyl]-9-phenyl-9 H -carbazole (abbreviation: PCPN), 9-[4-(10-phenyl-9-anthracenyl)phenyl]-9 H -carbazole (abbreviation: CzPA), 7- [4- (10-phenyl-9-anthryl) phenyl] -7 H - dibenzo [c, g] carbazole (abbreviation: cgDBCzPA), 6- [3- (9,10-diphenyl-2-not Trill) phenyl] benzo [b] naphtho [1,2- d] furan (abbreviation: 2mBnfPPA), and 9-phenyl-10- {4- (9-phenyl -9 H-fluoren-9-yl) -Biphenyl-4'-yl}anthracene (abbreviation: FLPPA) is included. In particular, CzPA, cgDBCzPA, 2mBnfPPA, and PCzPA are preferred choices because of their excellent properties.

Further, it is particularly preferable that the light-emitting device of one embodiment of the present invention is applied to a light-emitting device that emits blue fluorescence.

Further, the host material may be a mixture of a plurality of types of substances, and when a mixed host material is used, it is preferable to mix a material having electron transport properties with a material having hole transport properties. By mixing a material having electron transport properties with a material having hole transport properties, the transport properties of the light emitting layer 113 can be easily controlled and the recombination region can be easily controlled. The ratio of the content of the material having the hole transport property and the content of the material having the electron transport property may be 1:9 to 9:1.

An excited composite may be formed from these mixed materials. When a combination of these materials is selected so that an excited composite that emits light having a wavelength that overlaps with the wavelength of the lowest energy absorption band of the light emitting material is selected, energy is smoothly transferred, light emission can be efficiently obtained, and the driving voltage is reduced. It is preferable because it is reduced.

The electron transport layer 114 is a layer including a material having electron transport properties. As the substance having electron transport properties, any of the above-described substances having electron transport properties that can be used as a host material can be used.

Between the electron transport layer 114 and the cathode 102, as the electron injection layer 115, an alkali metal such as lithium fluoride (LiF), cesium fluoride (CsF), or calcium fluoride (CaF _{2 ), alkaline earth metal} Or, you may provide a layer containing these compounds. For example, an electron injection layer 115 may be formed using an electron or a material having electron transport properties and including an alkali metal, an alkaline earth metal, or a compound thereof. Examples of electrons include a material in which electrons are added in a high concentration to a mixture of calcium and aluminum oxide (calcium oxide-aluminum oxide).

Instead of the electron injection layer 115, a charge generation layer 116 may be provided (see Fig. 1B). The charge generation layer 116 refers to a layer capable of injecting holes into a layer contacting the cathode side of the charge generation layer 116 when a potential is applied and electrons into the layer contacting the anode side. The charge generation layer 116 includes at least a p-type layer 117. The p-type layer 117 is preferably formed using any of the above-described composite materials as an example of a material that can be used for the hole injection layer 111. The p-type layer 117 may be formed by laminating a film containing the above-described acceptor material and a film containing a hole transport material as a material included in the composite material. When a potential is applied to the p-type layer 117, electrons are injected into the electron transport layer 114 and holes are injected into the cathode 102 functioning as a cathode, so that the light emitting element is operated.

In addition, the charge generation layer 116 preferably includes one or both of the electron relay layer 118 and the electron injection buffer layer 119 in addition to the p-type layer 117.

The electronic relay layer 118 includes at least a material having electron transport properties, and has a function of preventing interaction between the electron injection buffer layer 119 and the p-type layer 117 and smoothly transporting electrons. The LUMO level of the electron transporting material included in the electron relay layer 118 is the LUMO level of the acceptor material in the p-type layer 117 and the charge generation layer 116 of the electron transport layer 114. It is preferably between the LUMO levels of the material contained in the layer. As a specific value of the energy level, the LUMO level of the substance having electron transport properties in the electron relay layer 118 is preferably -5.0 eV or more, and more preferably -5.0 eV or more and -3.0 eV or less. In addition, it is preferable to use a phthalocyanine-based material or a metal complex having a metal-oxygen bond and an aromatic ligand as a material having electron transport properties in the electromagnetic relay layer 118.

A material having high electron injection properties may be used for the electron injection buffer layer 119. For example, alkali metals, alkaline earth metals, rare earth metals, or compounds thereof (e.g., alkali metal compounds (including oxides such as lithium oxide, halides, and carbonates such as lithium carbonate or cesium carbonate)) , Alkaline earth metal compounds (including oxides, halides, and carbonates), or rare earth metal compounds (including oxides, halides, and carbonates) may be used.

When the electron injection buffer layer 119 includes a material having electron transport properties and a donor material, an alkali metal, an alkaline earth metal, a rare earth metal, and a compound of the above-described metal (e.g., an alkali metal compound (oxide such as lithium oxide, Including lozenides and carbonates such as lithium carbonate or cesium carbonate), alkaline earth metal compounds (including oxides, halides, and carbonates), and rare earth metal compounds (including oxides, halides, and carbonates) )), an organic compound such as tetrathianapthacene (abbreviation: TTN), nickellocene, or decamethylnickelocene can be used as a donor material. Further, as the material having electron transport properties, a material similar to the above-described material used for the electron transport layer 114 can be used.

As the cathode 102, for example, any of a metal having a low work function (specifically, 3.8 eV or less), an alloy, an electrically conductive compound, and a mixture thereof may be used. Specific examples of such negative electrode materials include alkali metals (e.g., lithium (Li) and cesium (Cs)), magnesium (Mg), calcium (Ca), and strontium (Sr). There are elements belonging to Group 2, their alloys (eg, MgAg and AlLi), rare earth metals such as europium (Eu) and ytterbium (Yb), and alloys thereof. However, in the case of providing an electron injection layer between the cathode 102 and the electron transport layer, for the cathode 102, among various conductive materials such as Al, Ag, ITO, or indium oxide-tin oxide including silicon or silicon oxide. Anything can be used regardless of the work function. Films of these conductive materials can be formed by a dry method such as a vacuum vapor deposition method or a sputtering method, an ink jet method, a spin coating method, or the like. Further, the film may be formed by a wet method using a sol-gel method, or may be formed by a wet method using a paste of a metal material.

Regardless of whether it is a dry process or a wet process, any of a variety of methods can be used for forming the EL layer 103. For example, a vacuum evaporation method, a gravure printing method, an offset printing method, a screen printing method, an inkjet method, or a spin coating method may be used.

The electrodes or layers described above may be formed by other methods.

The configuration of the layer provided between the anode 101 and the cathode 102 is not limited to the above-described configuration. In order to suppress quenching due to the proximity of the light emitting region to the electrode and the metal used for the carrier injection layer, it is preferable that the light emitting region where holes and electrons are recombined are located away from the anode 101 and the cathode 102.

In addition, the hole transport layer and the electron transport layer in contact with the light emitting layer 113, in particular, a carrier transport layer close to the recombination region of the light emitting layer 113, in order to suppress the energy transfer from excitons generated in the light emitting layer, are a light emitting material or a light emitting layer of the light emitting layer. It is preferable that it is formed using a material having a wider band gap than the light emitting material contained in the material.

Next, an embodiment of a light-emitting device having a configuration in which a plurality of light-emitting units are stacked (a light-emitting device of this type is also referred to as a stacked device or a tandem device) will be described with reference to FIG. 1C. In this light-emitting element, a plurality of light-emitting units are provided between the anode and the cathode. One light-emitting unit has substantially the same configuration as the EL layer 103 shown in Fig. 1A. In other words, the light-emitting element shown in FIG. 1C is a light-emitting element including a plurality of light-emitting units, and each light-emitting element shown in FIGS. 1A and 1B includes one light-emitting unit. It is a light-emitting device.

In FIG. 1C, a first light emitting unit 511 and a second light emitting unit 512 are stacked between the anode 501 and the cathode 502, and the first light emitting unit 511 and the second light emitting unit A charge generation layer 513 is provided between 512. The positive electrode 501 and the negative electrode 502 correspond to the positive electrode 101 and the negative electrode 102 shown in FIG. 1A, respectively, and the materials suggested in the description of FIG. 1A may be used. . Further, the first light-emitting unit 511 and the second light-emitting unit 512 may have the same configuration or different configurations.

When a voltage is applied between the anode 501 and the cathode 502, the charge generation layer 513 has a function of injecting electrons into one of the light emitting units and injecting holes into the other of the light emitting units. That is, in FIG. 1C, when a voltage is applied so that the potential of the anode is higher than the potential of the cathode, the charge generation layer 513 transfers electrons to the first light emitting unit 511 and the second light emitting unit 512. Holes are injected into the

It is preferable that the charge generation layer 513 has a configuration similar to that of the charge generation layer 116 described with reference to FIG. 1B. Since the composite material of an organic compound and a metal oxide is excellent in carrier injection property and carrier transport property, low voltage drive or low current drive can be realized. In addition, when the surface on the anode side of the light emitting unit is in contact with the charge generation layer 513, the charge generation layer 513 can also function as a hole injection layer in the light emitting unit, so that a hole injection layer must be formed in the light emitting unit. There is no need.

When the electron injection buffer layer 119 is provided, the electron injection buffer layer 119 functions as an electron injection layer in the light emitting unit on the anode side, so that the light emitting unit on the anode side does not require an electron injection layer.

Although a light-emitting element having two light-emitting units has been described with reference to FIG. 1C, the present invention can be similarly applied to a light-emitting element in which three or more light-emitting units are stacked. A device having a long lifespan capable of emitting light with high luminance while maintaining a low current density by dividing a plurality of light emitting units between a pair of electrodes by the charge generation layer 513, as in the light emitting device according to the present embodiment. Can provide. In addition, a light-emitting device driven by a low voltage and low power consumption can be manufactured.

In addition, if the emission colors of the light-emitting units are different, light emission of a desired color can be obtained as a whole light-emitting element. For example, in a light-emitting element having two light-emitting units, if the light-emitting colors of the first light-emitting unit are red and green and the light-emitting color of the second light-emitting unit is blue, the light-emitting element may emit white light as the whole element.

The above-described electrodes and layers such as the EL layer 103, the first light-emitting unit 511, the second light-emitting unit 512, and the charge generation layer are a vapor deposition method (including a vacuum vapor deposition method), a droplet discharge method (inkjet It can be deposited by a method such as a method such as a method), a coating method, or a gravure printing method. A low-molecular material, a medium-molecular material (including an oligomer and a dendrimer), or a high-molecular material may be included in the layer and electrode.

Here, a method of forming the EL layer 786 by the droplet discharge method will be described with reference to FIGS. 34A to 34D. 34A to 34D are cross-sectional views showing a method of forming the EL layer 786.

First, a conductive film 772 is formed on the planarization insulating film 770, and the insulating film 730 is formed to cover a part of the conductive film 772 (see FIG. 34A).

Next, the droplet 784 is ejected from the droplet ejection device 783 to the exposed portion of the conductive layer 772 that is the opening of the insulating layer 730 to form a layer 785 containing the composition. The droplet 784 is a composition containing a solvent, and is attached to the conductive film 772 (see Fig. 34B).

Further, the step of discharging the droplet 784 may be performed under reduced pressure.

Next, the solvent is removed from the layer 785 containing the composition, and the layer is solidified to form the EL layer 786 (see Fig. 34C).

The solvent may be removed by drying or heating.

Next, a conductive film 788 is formed on the EL layer 786 to form a light emitting element 782 (see Fig. 34D).

When the EL layer 786 is formed by the droplet discharge method as described above, the composition can be selectively discharged, thereby reducing material waste. In addition, since a lithography process or the like for shaping is unnecessary, the process is simplified and the cost is reduced.

The above-described droplet discharging method is a generic term for droplet discharging means such as a nozzle having a discharging port of the composition or a head having one or more nozzles.

Next, a droplet ejection apparatus used in the droplet ejection method will be described with reference to FIG. 35. 35 is a conceptual diagram illustrating a droplet discharge device 1400.

The droplet ejection device 1400 includes droplet ejection means 1403. Further, the droplet discharging means 1403 includes a head 1405, a head 1412, and a head 1416.

Since the heads 1405, 1412, and 1416 are connected to the control means 1407 controlled by the computer 1410, a pattern programmed in advance can be drawn.

Drawing may be performed, for example, at a timing based on the marker 1411 formed on the substrate 1402. Alternatively, a reference point may be determined based on the outer end of the substrate 1402. Here, the marker 1411 is detected by the imaging means 1404, and converted into a digital signal by the image processing means 1409. After the digital signal is recognized by the computer 1410, a control signal is generated and transmitted to the control means 1407.

As the imaging means 1404, an image sensor using a charge-coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) can be used. In addition, information on the pattern to be formed on the substrate 1402 is stored in the storage medium 1408, and a control signal is transmitted to the control means 1407 based on this information, so that each head of the droplet ejection means 1403 (1405, 1412, and 1416) can be controlled independently. The material to be discharged is supplied from the material supply sources 1413, 1414, and 1415 to the heads 1405, 1412, and 1416 through piping, respectively.

Inside the head 1405, as indicated by the dotted line 1406, a space filled with a liquid material and a nozzle serving as a discharge port are provided. Although not shown, the internal structure of the heads 1412 and 1416 is similar to the internal structure of the head 1405. The heads 1405 and 1412 may simultaneously discharge different materials with different widths if the nozzle sizes are different. Each head can eject and draw a plurality of light-emitting materials. In the case of writing in a large area, the same material can be simultaneously discharged from a plurality of nozzles to improve throughput to perform writing. In the case of using a large-sized substrate, the heads 1405, 1412, and 1416 can freely scan the substrate in the directions indicated by arrows X, Y, and Z in FIG. 35, and freely set a region for drawing a pattern. Therefore, a plurality of the same patterns can be drawn on one substrate.

The step of discharging the composition may be performed under reduced pressure. Further, when discharging the composition, the substrate may be heated. After discharging the composition, one or both of drying and baking are performed. Both drying and baking are heat treatments, but the purpose, temperature, and time are different. The steps of drying and baking are performed by laser irradiation, instantaneous thermal annealing, or heating using a heating furnace under normal or reduced pressure. In addition, the timing of this heat treatment and the number of times of heat treatment are not particularly limited. The temperature for properly carrying out the steps of drying and baking depends on the properties of the material and composition of the substrate.

In the manner described above, the EL layer 786 can be formed using a droplet ejection device.

When the EL layer 786 is formed using a droplet ejection device, a hole transport layer can be formed by a wet method using a composition in which the hole transport material of the present invention is dissolved in a solvent. In this case, benzene, toluene, xylene, mesitylene, tetrahydrofuran, dioxane, ethanol, methanol, n -propanol, isopropanol, n -butanol, t -butanol, acetonitrile, dimethylsulfoxide, Various organic solvents such as dimethylformamide, chloroform, methylene chloride, carbon tetrachloride, ethyl acetate, hexane, and cyclohexane may be used to form the coating composition. In particular, benzene derivatives with low polarity, such as benzene, toluene, xylene, and mesitylene, can obtain a solution having an appropriate concentration, and prevent the hole transport material of the present invention contained in the ink from deteriorating due to oxidation, etc. It is desirable because there is. Further, in order to realize a uniform film or a film having a uniform thickness, it is preferable to use a solvent having a boiling point of 100°C or higher, and more preferably toluene, xylene, or mesitylene.

In addition, the above-described configuration can be appropriately combined with any of the configurations of this embodiment and other embodiments.

(Embodiment 2)

In this embodiment, an organic compound of one embodiment of the present invention will be described.

Some of the organic compounds described in Embodiment 1 that can be used as the second hole transport material are novel compounds, and are therefore one embodiment of the present invention. The organic compound of one embodiment of the present invention will be described below.

The organic compound of one embodiment of the present invention is represented by general formula (G1).

[Formula 7]

In addition, in the general formula (G1), R ¹ to R ⁸ are independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogenated group. It represents any one of a lozene, a C1-C6 haloalkyl group, and a substituted or unsubstituted C6-C60 aromatic hydrocarbon group.

^{Specific examples of R 1} to R ⁸ in General Formula (G1) are represented by Formulas (1-1) to (1-40). When R ¹ to R ⁸ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, the aromatic hydrocarbon of the skeleton of the substituent is represented by formulas (2-1) to (2-13). In addition, there is no restriction on the substitution position of the aromatic hydrocarbon represented by formulas (2-1) to (2-13), and a skeleton may be formed by connecting a plurality of aromatic hydrocarbon groups.

[Formula 8]

[Formula 9]

In addition, when R ¹ to R ⁸ are each an aromatic hydrocarbon group containing a substituent, the substituent is a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and cyano. Group, halogen, haloalkyl group having 1 to 6 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, dibenzofuranyl group, dibenzothiophenyl group, benzonaphthofuranyl group, and benzonaphthothio Any of the phenyl groups can be used. Each of R ¹ to R ⁸ is an aromatic hydrocarbon group containing a substituent, and the substituent is a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogen. , and the equation (1-1) to (1-40) shown above, if the carbon number of 1 to 6 by any of the haloalkyl group, a specific configuration example of R ¹ to R ⁸ is, as a specific example of R ¹ to R ⁸ It is the same as the configuration represented by.

R ¹ to R ⁸ are each an aromatic hydrocarbon group containing a substituent, and the substituent is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, a dibenzofuranyl group, a dibenzothiophenyl group, a benzonaphthofuranyl group, And in the case of any of a benzonaphthothiophenyl group, ^{specific examples of R 1} to R ⁸ are represented by formulas (1-41) to (1-81). In all of the substituents represented by formulas (1-41) to (1-81), there is no restriction on the substitution position.

[Formula 10]

[Formula 11]

One of A and B represents a group represented by the general formula (g1), and the other is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, halogen, and 1 to 6 carbon atoms. Represents a haloalkyl group, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. Specific examples are the same as the substituents R ¹ to R ⁸ .

[Formula 12]

Further, in the general formula (g1), Ar ¹ and Ar ² independently represent either a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms and a group represented by the general formula (g2). When Ar ¹ and Ar ² are each an aromatic hydrocarbon group having 6 to 60 carbon atoms and include a substituent, the substituent includes a benzonaphthofuranyl group and a dynapthofuranyl group.

[Formula 13]

In addition, in the general formula (g2), R ¹¹ to R ¹⁸ are independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a halogenated group. It represents any one of a lozene, a C1-C6 haloalkyl group, and a substituted or unsubstituted C6-C60 aromatic hydrocarbon group. One of Z ¹ and Z ² is bonded to a nitrogen atom in the general formula (g1), and the other is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a halogen, and a carbon number. Represents any one of a haloalkyl group having 1 to 6, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. ^{In addition, specific examples of R 11} to R ¹⁸ in the group represented by the general formula (g2) are ^{the same as R 1} to R ⁸ in the organic compound represented by the general formula (G1). ^{In addition, a specific example of one of Z 1} and Z ² not bonded to a nitrogen atom in the group represented by the general formula (g1) is an organic represented by the general formula (G1), which is not represented by the general formula (g1). It is the same as one of A and B in the compound. That is, in the group represented by the general formula (g1), ^{one of Z 1} and Z ² not bonded to a nitrogen atom is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, Represents any one of halogen, a C1-C6 haloalkyl group, a C1-C6 hydrocarbon group, and a substituted or unsubstituted C6-C60 aromatic hydrocarbon group. In addition, specific examples of these are the same as the substituents R ¹ to R ⁸ described above.

Examples of a specific skeleton of an aromatic hydrocarbon group having 6 to 60 carbon atoms that can be used as ^{Ar 1} and Ar ² in the general formula (g1) are skeletons represented by structural formulas (2-1) to (2-13). In addition, there is no restriction|limiting on the substitution position, Each group may consist of a plurality of skeletons.

[Formula 14]

^{In addition, when Ar 1} and Ar ² in the general formula (g1) are each an aromatic hydrocarbon group containing a substituent, the substituent is a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, and 6 alkoxy group, cyano group, halogen, C 1 to C 6 haloalkyl group, substituted or unsubstituted C 6 to C 60 aromatic hydrocarbon group, dibenzofuranyl group, dibenzothiophenyl group, benzonaphthofuranyl group , And a benzonaphthothiophenyl group. Ar ¹ and Ar ² are each an aromatic hydrocarbon group containing a substituent, and the substituent is a hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a halogen , And in the case of any of a haloalkyl group having 1 to 6 carbon atoms ^{, specific structural examples of Ar 1} and Ar ² are Formula (1-1) shown above as a specific example ^{of R 1} to R ⁸ in General Formula (G1) ) To (1-40).

^{Ar 1} and Ar ² in the general formula (g1) are each an aromatic hydrocarbon group containing a substituent, and the substituent is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, a dibenzofuranyl group, a dibenzothiophenyl group , ^{Benzonaphthofuranyl group, and benzonaphthothiophenyl group, specific examples of Ar 1} and Ar ² are represented by formulas (1-41) to (1-135). In all of the substituents represented by formulas (1-41) to (1-135), there is no restriction on the substitution position.

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

Specific examples of the substituent represented by formula (g2) are as follows.

[Formula 20]

[Formula 21]

[Formula 22]

Another aspect of the present invention is an organic compound, which is a group represented by the general formula (g1) and a group represented by the general formula (g3).

[Formula 23]

In addition, in the general formula (g3), Ar ³ and Ar ⁴ are independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, a substituted or unsubstituted benzonaphthofuranyl group, and a substituted or unsubstituted diner. Represents any one of the ptofuranyl groups. Ar ³ and Ar ⁴ are the same ^{as Ar 1} and Ar ² in the general formula (g1). In addition, ^{the sum of the carbon number of Ar 3} and Ar ⁵ is 60 or less, and the sum of the carbon number of Ar ⁴ and Ar ⁶ is 60 or less.

Ar ⁵ and Ar ⁶ independently represent a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 54 carbon atoms, and n and m independently represent 0 to 2. In addition, ^{the sum of the carbon number of Ar 3} and Ar ⁵ is 60 or less, and the sum of the carbon number of Ar ⁴ and Ar ⁶ is 60 or less. A specific example of Ar ⁵ and Ar ⁶ is a divalent group having a skeleton represented by structural formulas (2-1) to (2-13).

[Formula 24]

In the organic compound having the above-described configuration, Ar ³ and Ar ⁴ are each of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, and a substituted or unsubstituted pyrenyl group. When one is shown, it is preferable because a transport layer having high heat resistance and good film quality and good hole transport properties can be obtained. In particular, when ^{each of Ar 3} and Ar ⁴ represents a phenyl group, it is preferable because a layer having good hole transport properties can be efficiently deposited.

In the organic compound having the above-described configuration, Ar ⁵ and Ar ⁶ are each a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, and a substituted or unsubstituted pyrene When any one of the yylene groups is shown, it is preferable because it can provide a transport layer having high heat resistance, good film quality, and good hole transport properties. In particular, when ^{each of Ar 5} and Ar ⁶ represents a phenylene group, it is preferable because a layer having good hole transport properties can be efficiently deposited.

In the organic compound having the above-described configuration, when one of n and m is 1 and the other is 0, a high-quality film having good hole transport properties is realized, and thus it is particularly preferable.

Specific examples of the organic compound having the above-described configuration are as follows.

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Chemical Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Chemical Formula 36]

[Chemical Formula 37]

[Formula 38]

[Chemical Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Formula 46]

[Chemical Formula 47]

The organic compounds described above can be synthesized according to the synthesis schemes (a-1), (a-2), (b-1), and (b-2) shown below.

A method for synthesizing the organic compound represented by General Formula (G1) will be described. In the general formula (G1), R ¹ to R ⁸ are independently hydrogen, a C 1 to C 6 hydrocarbon group, a C 3 to C 6 cyclic hydrocarbon group, a C 1 to C 6 alkoxy group, a cyano group, a halogen , A haloalkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. One of A and B represents a group represented by the general formula (g1), and the other is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, halogen, and 1 to 6 carbon atoms. Represents a haloalkyl group, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms.

[Formula 48]

Further, in the general formula (g1), Ar ¹ and Ar ² independently represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. When Ar ¹ and Ar ² each contain a substituent, the substituent includes a benzonaphthofuranyl group and a dynapthofuranyl group.

[Formula 49]

Therefore, general formula (G1) can be represented by general formula (G1-a) or (G1-b). Various reactions can be applied to the synthesis method of the organic compound represented by the general formulas (G1-a) and (G1-b). In addition, the synthesis method of the organic compound of one embodiment of the present invention represented by the general formulas (G1-a) and (G1-b) is not limited to the following synthesis method.

[Formula 50]

[Formula 51]

<Method for synthesizing an organic compound represented by general formula (G1-a)>

The organic compound of one embodiment of the present invention represented by the general formula (G1-a) can be synthesized according to the synthesis scheme (a-1) or (a-2) shown below.

That is, by combining a benzonaphthofuran compound (Compound 1) with a diarylamine (Compound 2), a benzonaphthofuranylamino compound (G1-a) can be obtained. Alternatively, a benzonaphthofuranylamino compound (G1-a) can be obtained by combining benzonaphthofuranylamine (Compound 3) with a compound having an aryl skeleton (Compound 4). Synthesis schemes (a-1) and (a-2) are shown below.

[Formula 52]

[Chemical Formula 53]

In the synthesis schemes (a-1) and (a-2), R ¹ to R ⁸ are independently hydrogen, a C 1 to C 6 hydrocarbon group, a C 3 to C 6 cyclic hydrocarbon group, and a C 1 to C 6 alkoxy A group, a cyano group, a halogen, a haloalkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. A is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a halogen, a haloalkyl group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted Represents any one of an aromatic hydrocarbon group having 6 to 60 carbon atoms. Ar ¹ and Ar ² independently represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. When Ar ¹ and Ar ² each contain a substituent, the substituent includes a benzonaphthofuranyl group and a dynapthofuranyl group, and does not include an amino group.

X ¹ and X ⁴ independently represent chlorine, bromine, iodine, or a triflate group, and X ² and X ³ independently represent hydrogen or an organic tin group.

In the synthesis schemes (a-1) and (a-2), when applying the Buchwald-Hartwig reaction using a palladium catalyst, bis(dibenzylideneacetone)palladium(0), palladium(II) acetate, [1 ,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, tetrakis(triphenylphosphine)palladium(0), or allylpalladium(II)chloride(dimer), and other palladium compounds, and tri( tert -butyl)phosphine, tri( n -hexyl)phosphine, tricyclohexylphosphine, di(1-adamantyl) -n -butylphosphine, 2-dicyclohexylphosphino-2',6' -Dimethoxybiphenyl , tri(ortho-tolyl)phosphine, or (S)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diisopropylphosphine)( Abbreviation: A ligand such as cBRIDP (registered trademark)) can be used. In the above reaction, an organic base such as sodium tert -butoxide, or an inorganic base such as potassium carbonate, cesium carbonate, or sodium carbonate may be used. In the above reaction, toluene, xylene, benzene, tetrahydrofuran, dioxane, or the like can be used as a solvent. Reagents that can be used in the reaction are not limited to the above-described reagents.

When the Ulman reaction using copper or a copper compound is carried out in the synthesis schemes (a-1), (a-2), and (b-1), X ¹ and X ⁴ are independently chlorine, bromine, or child. Represents odine, and X ² and X ³ represent hydrogen. Copper or copper compounds can be used in the reaction. Examples of the base to be used include inorganic bases such as potassium carbonate. Examples of solvents that can be used in the reaction include 1,3-dimethyl-3,4,5,6-tetrahydro-2( 1H )pyrimidinone (DMPU), toluene, xylene, and benzene. do. In the Ullman reaction, it is preferable to use DMPU or xylene with a high boiling point, since a reaction temperature of 100° C. or higher can obtain a desired product in a shorter time and in a higher yield. Since it is more preferable that the reaction temperature is 150° C. or higher, it is more preferable to use DMPU. Reagents that can be used in the reaction are not limited to the above-described reagents.

<Method for synthesizing an organic compound represented by general formula (G1-b)>

The organic compound of the present invention represented by the general formula (G1-b) can be synthesized according to the synthesis scheme (b-1) or (b-2) shown below.

That is, by combining a benzonaphthofuran compound (Compound 5) with a diarylamine (Compound 6), a benzonaphthofuranylamino compound (G1-b) can be obtained. Alternatively, a benzonaphthofuranylamino compound (G1-b) can be obtained by combining benzonaphthofuranylamine (Compound 7) with a compound having an aryl skeleton (Compound 8). Synthesis schemes (b-1) and (b-2) are shown below.

[Chemical Formula 54]

[Chemical Formula 55]

In the synthesis schemes (b-1) and (b-2), R ¹ to R ⁸ are independently hydrogen, a C 1 to C 6 hydrocarbon group, a C 3 to C 6 cyclic hydrocarbon group, and a C 1 to C 6 alkoxy A group, a cyano group, a halogen, a haloalkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. A is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a halogen, a haloalkyl group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted Represents any one of an aromatic hydrocarbon group having 6 to 60 carbon atoms. Ar ¹ and Ar ² independently represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms. When Ar ¹ and Ar ² each contain a substituent, the substituent includes a benzonaphthofuranyl group and a dynapthofuranyl group, and does not include an amino group.

X ¹ and X ⁴ independently represent chlorine, bromine, iodine, or a triflate group, and X ² and X ³ independently represent hydrogen or an organic tin group.

In the synthesis schemes (b-1) and (b-2), when applying the Buchwald-Hartwig reaction using a palladium catalyst, bis(dibenzylideneacetone)palladium(0), palladium(II) acetate, [1 ,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, tetrakis(triphenylphosphine)palladium(0), or allylpalladium(II)chloride(dimer), and other palladium compounds, and tri ( tert -butyl)phosphine, tri( n -hexyl)phosphine, tricyclohexylphosphine, di(1-adamantyl) -n -butylphosphine, 2-dicyclohexylphosphino-2',6 '-Dimethoxybiphenyl , tri(ortho-tolyl)phosphine, or (S)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diisopropylphosphine) A ligand such as (abbreviation: cBRIDP (registered trademark)) can be used. In the above reaction, an organic base such as sodium tert -butoxide, or an inorganic base such as potassium carbonate, cesium carbonate, or sodium carbonate may be used. In the above reaction, toluene, xylene, benzene, tetrahydrofuran, dioxane, or the like can be used as a solvent. Reagents that can be used in the reaction are not limited to the above-described reagents.

When the Ulman reaction using copper or a copper compound is carried out in the synthesis schemes (b-1) and (b-2), X ¹ and X ⁴ independently represent chlorine, bromine, or iodine, and X ² and X ³ represents hydrogen. Copper or copper compounds can be used in the reaction. Examples of the base to be used include inorganic bases such as potassium carbonate. Examples of solvents that can be used in the reaction include 1,3-dimethyl-3,4,5,6-tetrahydro-2( 1H )pyrimidinone (DMPU), toluene, xylene, and benzene. do. In the Ullman reaction, it is preferable to use DMPU or xylene with a high boiling point, since a reaction temperature of 100° C. or higher can obtain a desired product in a shorter time and in a higher yield. Since it is more preferable that the reaction temperature is 150° C. or higher, it is more preferable to use DMPU. Reagents that can be used in the reaction are not limited to the above-described reagents.

(Embodiment 3)

In this embodiment, a light-emitting device including the light-emitting element described in the first embodiment will be described.

In this embodiment, a light-emitting device manufactured using the light-emitting element described in the first embodiment will be described with reference to Figs. 2A and 2B. In addition, FIG. 2A is a top view of the light emitting device, and FIG. 2B is a cross-sectional view taken along lines A-B and C-D of FIG. 2A. This light-emitting device includes a driving circuit portion (source line driving circuit) 601, a pixel portion 602, and a driving circuit portion (gate line driving circuit) 603 shown by dotted lines, which control light emission of light-emitting elements. . Reference numeral 604 denotes a sealing substrate, 605 denotes a sealing material, and 607 denotes a space surrounded by the sealing material 605.

Reference numeral 608 denotes a video signal, a clock signal, and a start from a flexible printed circuit (FPC) 609 that transmits signals input to the source line driving circuit 601 and the gate line driving circuit 603, and functions as external input terminals. A wiring for receiving signals, such as a signal and a reset signal, is shown. Although only the FPC is shown here, a printed wiring board (PWB) may be attached to the FPC. The light-emitting device of the present specification includes not only the light-emitting device itself, but also a light-emitting device provided with FPC or PWB in its category.

Next, a cross-sectional structure will be described with reference to Fig. 2B. A driving circuit portion and a pixel portion are formed on the element substrate 610, and FIG. 2B shows a source line driving circuit 601, which is a driving circuit portion, and one pixel in the pixel portion 602. In FIG.

The device substrate 610 may be a substrate including glass, quartz, organic resin, metal, alloy, or semiconductor, or made of fiber reinforced plastic (FRP), poly(vinyl fluoride) (PVF), polyester, or acrylic. It may be a formed plastic substrate.

The structure of the transistor used in the pixel and the driving circuit is not particularly limited. For example, an inverse stagger type transistor may be used, or a stagger type transistor may be used. Further, a top-gate transistor or a bottom-gate transistor may be used. The semiconductor material used for the transistor is not particularly limited, and, for example, silicon, germanium, silicon carbide, gallium nitride, or the like can be used. Alternatively, an oxide semiconductor containing at least one of indium, gallium, and zinc, such as an In-Ga-Zn-based metal oxide, may be used.

There is no particular limitation on the crystallinity of the semiconductor material used for the transistor, and an amorphous semiconductor or a semiconductor having crystalline properties (microcrystalline semiconductor, polycrystalline semiconductor, single crystal semiconductor, or semiconductor partially containing a crystalline region) may be used. . When a semiconductor having crystallinity is used, deterioration of transistor characteristics can be suppressed, which is preferable.

Here, it is preferable to use an oxide semiconductor for semiconductor devices such as transistors provided in pixels and driving circuits, and transistors used in touch sensors described later. In particular, it is preferable to use an oxide semiconductor having a wider band gap than silicon. If an oxide semiconductor with a band gap wider than that of silicon is used, the off-state current of the transistor can be reduced.

It is preferable that the oxide semiconductor contains at least indium (In) or zinc (Zn). The oxide semiconductor is more preferably an oxide represented by an In-M- Zn-based oxide ( M represents a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce, or Hf). .

It is particularly preferable to use an oxide semiconductor film including a plurality of crystal portions in which the c-axis is vertically oriented with respect to the surface on which the semiconductor layer is formed or the upper surface of the semiconductor layer, and adjacent crystal portions do not have a grain boundary, as the semiconductor layer.

By using such a material for the semiconductor layer, it is possible to provide a highly reliable transistor in which fluctuations in electrical characteristics are suppressed.

Since the off-state current of the transistor is low, the charge accumulated in the capacitor through the transistor including the above-described semiconductor layer can be maintained for a long time. If such a transistor is used for a pixel, the operation of the driving circuit can be stopped while maintaining the gradation of the image displayed in each display area. As a result, an electronic device with very low power consumption can be obtained.

For stable characteristics of the transistor, it is desirable to provide an underlying film. The underlying film may be formed in a single layer structure or a stacked structure using an inorganic insulating film such as a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a silicon nitride oxide film. Sputtering the underlying film, chemical vapor deposition (CVD) method (e.g., plasma CVD method, thermal CVD method, or MOCVD (metal organic CVD) method), atomic layer deposition (ALD) method, coating method, or printing method, etc. It can be formed by In addition, the underlying film is not necessarily provided.

Further, an FET 623 is shown as a transistor formed in the driving circuit portion 601. Further, a driving circuit may be formed using any of various circuits such as a CMOS circuit, a PMOS circuit, or an NMOS circuit. In this embodiment, a driver integrated type in which a driving circuit is formed on a substrate is illustrated, but the driving circuit is not necessarily formed on the substrate, and the driving circuit may be formed outside the substrate instead of on the substrate.

The pixel portion 602 includes a plurality of pixels including a switching FET 611, a current control FET 612, and an anode 613 electrically connected to the drain of the current control FET 612. One embodiment of the present invention is not limited to this structure. The pixel portion 602 may include a combination of three or more FETs and capacitor elements.

In addition, an insulator 614 is formed here using a positive photosensitive acrylic resin film so as to cover the end of the anode 613.

In order to improve the coverage with an EL layer or the like to be formed later, the insulating material 614 is formed to have a curved surface having a curvature at its upper end or lower end. For example, when using positive photosensitive acrylic as the material of the insulating material 614, it is preferable that only the upper end of the insulating material 614 has a curved surface having a radius of curvature (0.2 μm to 3 μm). As the insulator 614, a negative photosensitive resin or a positive photosensitive resin can be used.

On the anode 613, an EL layer 616 and a cathode 617 are formed. Here, as the material used for the anode 613, it is preferable to use a material having a high work function. For example, a single layer film such as an ITO film, an indium tin oxide film containing silicon, an indium oxide film containing 2 wt% to 20 wt% zinc oxide, a titanium nitride film, a chromium film, a tungsten film, a Zn film, or a Pt film , Lamination of a titanium nitride film and a film containing aluminum as a main component, or a lamination of three layers of a titanium nitride film, a film containing aluminum as a main component, and a titanium nitride film may be used. The stacked structure enables low wiring resistance and good ohmic contact.

The EL layer 616 is formed by any of various methods such as a vapor deposition method using a vapor deposition mask, an ink jet method, and a spin coating method. The EL layer 616 has the configuration described in the first embodiment. As another material included in the EL layer 616, a low-molecular compound or a high-molecular compound (including an oligomer or dendrimer) may be used.

As a material used for the cathode 617 formed on the EL layer 616, a material having a low work function (e.g., Al, Mg, Li, and Ca, or an alloy or compound thereof (MgAg, MgIn, or AlLi) Etc.)) is preferably used. When the light generated from the EL layer 616 passes through the cathode 617, a metal thin film and a transparent conductive film (for example, ITO, indium oxide containing 2wt% to 20wt% zinc oxide, indium containing silicon) A stack of tin oxide or zinc oxide (ZnO) is preferably used for the cathode 617.

Further, the light emitting element is formed of an anode 613, an EL layer 616, and a cathode 617. The light-emitting element is the light-emitting element described in Embodiment 1. In the light-emitting device of this embodiment, the pixel portion including a plurality of light-emitting elements may include both the light-emitting elements described in the first embodiment and light-emitting elements having different configurations.

The sealing substrate 604 is adhered to the element substrate 610 with the sealing material 605, and the light emitting element 618 is placed in the space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealing material 605. ). The space 607 may be filled with a filler, or may be filled with an inert gas (such as nitrogen or argon) or a sealing material. If a concave portion is provided in the sealing substrate and a desiccant is provided in the concave portion, it is preferable to suppress deterioration due to the influence of moisture.

It is preferable to use an epoxy resin or a glass frit for the sealing material 605. It is preferred that such materials are as impermeable as possible to moisture or oxygen. As the sealing substrate 604, a glass substrate, a quartz substrate, or a plastic substrate formed of fiber reinforced plastic (FRP), poly(vinyl fluoride) (PVF), polyester, or acrylic can be used.

Although not shown in Figs. 2A and 2B, a protective film may be provided over the cathode. As the protective film, an organic resin film or an inorganic insulating film may be formed. The protective film may be formed so as to cover the exposed portion of the sealing material 605. The protective film may be provided so as to cover the surfaces and side surfaces of the pair of substrates, and exposed side surfaces such as a sealing layer and an insulating layer.

The protective film can be formed using a material that does not readily permeate impurities such as water. Therefore, it is possible to effectively suppress diffusion of impurities such as water from the outside to the inside.

As the material of the protective film, oxides, nitrides, fluorides, sulfides, ternary compounds, metals, polymers, and the like can be used. For example, the material is aluminum oxide, hafnium oxide, hafnium silicate, lanthanum oxide, silicon oxide, strontium titanate, tantalum oxide, titanium oxide, zinc oxide, neodymium oxide, zirconium oxide, tin oxide, yttrium oxide, oxide Cerium, scandium oxide, erbium oxide, vanadium oxide, indium oxide, aluminum nitride, hafnium nitride, silicon nitride, tantalum nitride, titanium nitride, neodymium nitride, molybdenum nitride, zirconium nitride, gallium nitride, titanium and aluminum. Nitride, oxides including titanium and aluminum, oxides including aluminum and zinc, sulfides including manganese and zinc, sulfides including cerium and strontium, oxides including erbium and aluminum, or yttrium and zirconium It may contain an oxide or the like.

The protective film is preferably formed using a deposition method having good step coverage. One of these methods is ALD (atomic layer deposition). It is preferable to use a material that can be deposited by the ALD method for the protective film. By the ALD method, defects such as cracks or pinholes are reduced, and a protective film having a uniform thickness and a compact thickness can be formed. In addition, damage to the processing member during formation of the protective film can be reduced.

By the ALD method, it is possible to form a uniform protective film with few defects on a surface having a complex uneven shape, or even on the upper surface, side surface, and lower surface of the touch panel.

As described above, a light-emitting device manufactured using the light-emitting element described in Embodiment 1 can be obtained.

Since the light-emitting device in this embodiment is manufactured using the light-emitting element described in the first embodiment, it can have good characteristics. Specifically, since the light-emitting element described in the first embodiment has a long life, it is possible to obtain a highly reliable light-emitting device. Since the light-emitting device using the light-emitting element described in Embodiment 1 has high luminous efficiency, a light-emitting device with low power consumption can be realized.

3A and 3B show examples of light-emitting devices in which full-color display is realized by forming a light-emitting element that emits white light and using a colored layer (color filter), respectively. 3A shows a substrate 1001, a base insulating film 1002, a gate insulating film 1003, a gate electrode 1006, 1007, and 1008, a first interlayer insulating film 1020, and Two interlayer insulating film 1021, peripheral portion 1042, pixel portion 1040, driving circuit portion 1041, anodes 1024W, 1024R, 1024G, and 1024B of light-emitting elements, partition 1025, EL layer 1028, The cathode 1029 of the light emitting element, the sealing substrate 1031, the sealing material 1032, and the like are shown.

In FIG. 3A, a colored layer (red colored layer 1034R, green colored layer 1034G, and blue colored layer 1034B) is provided on the transparent substrate 1033. A black matrix 1035 may be additionally provided. A transparent substrate 1033 provided with a colored layer and a black matrix is disposed and fixed to the substrate 1001. Further, the colored layer and the black matrix 1035 are covered with an overcoat layer 1036. In Fig. 3A, light emitted from a part of the light-emitting layer does not pass through the colored layer, and light emitted from another part of the light-emitting layer passes through the colored layer. Since the light that does not pass through the colored layer is white and the light that passes through any one of the colored layers is red, green, or blue, an image can be displayed using the four colored pixels.

3B shows an example in which a colored layer (red colored layer 1034R, green colored layer 1034G, and blue colored layer 1034B) is provided between the gate insulating film 1003 and the first interlayer insulating film 1020. Is shown. Like this structure, a colored layer may be provided between the substrate 1001 and the sealing substrate 1031.

The above-described light-emitting device is a light-emitting device having a structure in which light is extracted from the side of the substrate 1001 on which the FET is formed (bottom emission structure), but the structure in which light is extracted from the side of the sealing substrate 1031 It may be a light-emitting device having a (top emission structure). 4 is a cross-sectional view of a light emitting device having a top emission structure. In this case, a substrate that does not transmit light can be used as the substrate 1001. The process up to the step of forming a connection electrode connecting the FET and the anode of the light emitting element is performed in a manner similar to that of a light emitting device having a bottom emission structure. In addition, a third interlayer insulating film 1037 is formed to cover the electrode 1022. This insulating film may have a planarization function. The third interlayer insulating film 1037 may be formed using a material similar to that of the second interlayer insulating film, or may be formed using any of other known materials.

Here, the anodes 1024W, 1024R, 1024G, and 1024B of the light-emitting element each function as an anode, but may function as a cathode. Further, in the case of a light emitting device having a top emission structure as shown in FIG. 4, it is preferable that the anode is a reflective electrode. The EL layer 1028 is formed to have a structure similar to the structure of the EL layer 103 described in Embodiment 1, whereby white light emission can be obtained.

In the case of the top emission structure as shown in Fig. 4, sealing is performed with a sealing substrate 1031 provided with a colored layer (red colored layer 1034R, green colored layer 1034G, and blue colored layer 1034B). You can do it. The sealing substrate 1031 may be provided with a black matrix 1035 positioned between pixels. The colored layer (red colored layer 1034R, green colored layer 1034G, and blue colored layer 1034B) and the black matrix may be covered with an overcoat layer 1036. In addition, a light-transmitting substrate is used as the sealing substrate 1031. Here, an example of performing full-color display using four colors of red, green, blue, and white is shown, but there is no particular limitation, and there is no particular limitation, and there are four colors of red, yellow, green, and blue, or red, green, And full color display using three colors of blue may be performed.

In a light emitting device having a top emission structure, a microcavity structure can be preferably employed. A light-emitting element having a microcavity structure is formed using a reflective electrode as an anode and a transflective/reflective electrode as a cathode. A light-emitting element having a microcavity structure includes at least an EL layer including at least a light-emitting layer serving as a light-emitting region between a reflective electrode and a transflective/reflective electrode.

Further, the reflective electrode has a reflectance of visible light of 40% to 100%, preferably 70% to 100%, and a resistivity of 1×10 ^-2 Ωcm or less. Further, the transflective/reflective electrode has a transmittance of 20% to 80%, preferably 40% to 70% of visible light, and a resistivity of 1×10 ^-2 Ωcm or less.

Light emitted from the light-emitting layer included in the EL layer is reflected by the reflective electrode and the semi-transmissive/reflective electrode and resonates.

In the light-emitting element, the length of the optical path between the reflective electrode and the transflective/reflective electrode can be changed by changing the thickness of the transparent conductive film, the composite material, and the carrier transport material. Therefore, light having a wavelength that resonates between the reflective electrode and the semi-transmissive/reflective electrode can be strengthened, and light having a wavelength that does not resonate between them can be weakened.

Further, light reflected by the reflective electrode and returned (first reflected light) significantly interferes with light (first incident light) directly entering the semi-transmissive/reflective electrode from the light-emitting layer. For this reason, it is preferable to adjust the length of the optical path between the reflective electrode and the light emitting layer to (2 n -1) λ/4 ( n is a natural number of 1 or more and λ is the wavelength of the color to be amplified). By adjusting the length of the optical path, the phases of the first reflected light and the first incident light are matched with each other, and light emitted from the light emitting layer may be further amplified.

Further, in the above-described configuration, the EL layer may include a plurality of light-emitting layers or may include a single-layered light-emitting layer. The above-described tandem light-emitting element may be combined with a plurality of EL layers, for example, in the light-emitting element, a plurality of EL layers are provided, a charge generation layer is provided between the EL layers, and each EL layer is a plurality of light-emitting layers or a single layer. It may have a configuration including a light emitting layer of.

Due to the microcavity structure, it is possible to increase the light emission intensity of a specific wavelength in the front direction, thereby reducing power consumption. In addition, in the case of a light emitting device that displays an image with subpixels of four colors of red, yellow, green, and blue, the luminance can be increased by yellow light emission, and each subpixel is suitable for the wavelength of the corresponding color. Since the microcavity structure can be employed, the light emitting device can have good properties.

Since the light-emitting device in this embodiment is manufactured using the light-emitting element described in the first embodiment, it can have good characteristics. Specifically, since the light-emitting element described in Embodiment 1 has a long life, a light-emitting device with high reliability can be obtained. Since the light-emitting device using the light-emitting element described in Embodiment 1 has high luminous efficiency, a light-emitting device with low power consumption can be realized.

The active matrix light emitting device has been described above, but the passive matrix light emitting device is described below. 5A and 5B show a passive matrix light emitting device fabricated using the present invention. In addition, FIG. 5A is a perspective view of a light emitting device, and FIG. 5B is a cross-sectional view taken along line X-Y of FIG. 5A. In FIGS. 5A and 5B, an EL layer 955 is provided between the electrode 952 and the electrode 956 on the substrate 951. The end of the electrode 952 is covered with an insulating layer 953. A partition wall layer 954 is provided on the insulating layer 953. The sidewalls of the partition wall layer 954 are inclined so that the distance between both sidewalls gradually narrows toward the substrate surface. In other words, the cross section taken along the short side direction of the partition wall layer 954 is a trapezoid, and the bottom side (the side of the trapezoid that is parallel to the surface of the insulating layer 953 and in contact with the insulating layer 953) is the upper side (the insulating layer ( 953) and shorter than the trapezoidal side that does not contact the insulating layer 953). Accordingly, defects of the light emitting device due to static electricity or the like can be prevented by the provided barrier layer 954. Since the passive matrix light-emitting device also includes the light-emitting element described in Embodiment 1, it is possible to provide a light-emitting device with high reliability and low power consumption.

In the above-described light-emitting device, since a plurality of fine light-emitting elements arranged in a matrix can be individually controlled, the light-emitting device can be suitably used as a display device for displaying an image.

This embodiment can be freely combined with any of the other embodiments.

(Embodiment 4)

In this embodiment, an example in which the light-emitting element described in the first embodiment is used in a lighting device will be described with reference to Figs. 6A and 6B. 6B is a top view of the lighting device, and FIG. 6A is a cross-sectional view taken along the line e-f in FIG. 6B.

In the lighting device of this embodiment, the anode 401 is formed on the substrate 400 which is a support and has a light-transmitting property. The anode 401 corresponds to the anode 101 of the first embodiment. When light is extracted through the anode 401 side, the anode 401 is formed using a light-transmitting material.

On the substrate 400, a pad 412 for applying a voltage to the cathode 404 is provided.

An EL layer 403 is formed over the anode 401. The configuration of the EL layer 403 corresponds to, for example, the configuration of the EL layer 103 in Embodiment 1 or a configuration in which the light emitting units 511 and 512 and the charge generation layer 513 are combined. Refer to the above description for this configuration.

A cathode 404 is formed so as to cover the EL layer 403. The cathode 404 corresponds to the cathode 102 in the first embodiment. The cathode 404 is formed using a highly reflective material when light is extracted through the anode 401 side. The cathode 404 is connected to the pad 412 to apply a voltage.

As described above, the lighting device described in this embodiment includes a light emitting element including an anode 401, an EL layer 403, and a cathode 404. Since the light-emitting element is a light-emitting element with high luminous efficiency, the lighting device in this embodiment can be a lighting device with low power consumption.

The lighting device is completed by fixing and sealing the substrate 400 provided with the light emitting element having the above-described configuration to the sealing substrate 407 by the sealing materials 405 and 406. Only one of the sealing material 405 or the sealing material 406 may be used. Since the inner sealing material 406 (not shown in Fig. 6B) can be mixed with a desiccant and can adsorb moisture, reliability is improved.

If a portion of the pad 412 and the anode 401 extends outside the sealing materials 405 and 406, the extended portion can function as an external input terminal. An IC chip 420 on which a converter or the like is mounted may be provided on the external input terminal.

Since the lighting device described in the present embodiment includes the light-emitting element described in the first embodiment as an EL element, a light-emitting device with high reliability can be obtained. Further, it is possible to provide a light-emitting device with low power consumption.

(Embodiment 5)

In this embodiment, examples of electronic devices each including the light emitting elements described in the first embodiment will be described. The light emitting device described in Embodiment 1 has a long life and high reliability. As a result, the electronic devices described in the present embodiment may each include light emitting units having high reliability.

Examples of electronic devices to which the above-described light emitting element is applied include television devices (also referred to as TVs or television receivers), monitors for computers, cameras such as digital cameras and digital video cameras, digital photo frames, and mobile phones (cell phones or mobile phones Device), a portable game machine, a portable information terminal, a sound reproduction device, and a large game machine such as a pachinko device. Specific examples of these electronic devices are shown below.

7A shows an example of a television device. In the television apparatus, a display portion 7103 is incorporated in a housing 7101. Here, the housing 7101 is supported by a stand 7105. An image can be displayed on the display portion 7103, and in the display portion 7103, the light-emitting elements described in the first embodiment are arranged in a matrix.

The television apparatus can be operated by an operation switch of the housing 7101 or a separate remote controller 7110. The channel and volume can be controlled by the operation keys 7109 of the remote controller 7110, and an image displayed on the display portion 7103 can be controlled. The remote controller 7110 may be provided with a display portion 7107 for displaying data output from the remote controller 7110.

Further, the television apparatus is provided with a receiver, a modem, and the like. Using the receiver, it is possible to receive general television broadcasts. In addition, when a television apparatus is connected to a wired or wireless communication network through a modem, information communication in one-way (from a sender to a receiver) or two-way (between a sender and a receiver or between a receiver) can be performed.

7(B1) shows a computer including a main body 7201, a housing 7202, a display portion 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like. . Further, this computer is fabricated by arranging the light-emitting elements described in the first embodiment in a matrix on the display portion 7203. The computer shown in Fig. 7B1 may have the configuration shown in Fig. 7B2. The computer shown in FIG. 7B2 is provided with a second display portion 7210 instead of the keyboard 7204 and the pointing device 7206. The second display unit 7210 has a touch screen, and input can be performed by manipulating an image displayed on the second display unit 7210 with a finger or a dedicated pen. The second display unit 7210 may display an image other than the input display. The display portion 7203 may have a touch screen. By connecting the two screens with a hinge, it is possible to prevent the problem that the screen is scratched or damaged, for example, while storing or transporting the computer.

FIG. 7C shows a portable game machine having two housings, a housing 7301 and a housing 7302 connected by a connection part 7303 so that the portable game machine can be unfolded or folded. The housing 7301 includes a display portion 7304 in which the light-emitting elements described in the first embodiment are arranged in a matrix, and the housing 7302 includes a display portion 7305. In addition, the portable game machine shown in Fig. 7C is a speaker unit 7306, a recording medium insertion unit 7307, an LED lamp 7308, an input means (operation key 7309, a connection terminal 7310, and a sensor). (7311) (force, displacement, position, velocity, acceleration, angular velocity, rotational speed, distance, light, liquid, magnetic, temperature, chemical, negative, time, hardness, electric field, current, voltage, power, radiation, flow rate, A sensor having a function of measuring humidity, gradient, vibration, odor, or infrared rays), and a microphone 7312), and the like. Of course, the configuration of the portable game machine is not limited to the above, as long as the display portion in which the light emitting elements described in the first embodiment are arranged in a matrix is used for the display portion 7304 or the display portion 7305, or both. It may contain appendages as appropriate. The portable game machine shown in FIG. 7C has a function of reading a program or data stored in a recording medium and displaying it on a display unit, and a function of sharing information with another portable game device through wireless communication. In addition, the functions of the portable game machine shown in FIG. 7C are not limited to these, and the portable game machine may have various functions.

7D shows an example of a portable terminal. The mobile phone 7400 is provided with a display portion 7402, an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like built in the housing 7401. Further, the mobile phone 7400 has a display portion 7402 in which the light-emitting elements described in the first embodiment are arranged in a matrix.

When the display portion 7402 of the portable terminal shown in FIG. 7D is touched with a finger or the like, data can be input to the portable terminal. In this case, operations such as making a phone call or creating an email can be performed by touching the display portion 7402 with a finger or the like.

The display portion 7402 mainly has three screen modes. The first mode is a display mode mainly for displaying an image. The second mode is an input mode mainly for inputting information such as text. The third mode is a display and input mode in which two modes of a display mode and an input mode are combined.

For example, when making a phone call or writing an email, a text input mode may be selected for the display unit 7402 and text displayed on the screen may be input. In this case, it is preferable to display a keyboard or a number button on almost the entire screen of the display unit 7402.

If a detection device including a sensor such as a gyroscope or an acceleration sensor for detecting the inclination is provided in the portable terminal, the display unit 7402 is determined by determining the orientation of the portable terminal (whether the portable terminal is arranged horizontally or vertically). You can change the direction of the display on the screen automatically.

The screen mode is switched by touching the display portion 7402 or operating with an operation button 7403 of the housing 7401. The screen mode may be switched according to the type of image displayed on the display unit 7402. For example, if the signal of an image displayed on the display unit is a signal of moving picture data, the screen mode is switched to the display mode. If the signal is a signal of text data, the screen mode is switched to the input mode.

In addition, in the input mode, when a signal detected by the optical sensor of the display unit 7402 is detected and the input by the touch of the display unit 7402 is not performed for a certain period, the screen mode changes from the input mode to the display mode. It may be controlled as much as possible.

The display portion 7402 may function as an image sensor. For example, personal authentication may be performed by taking an image such as a palm print or a fingerprint while touching the display portion 7402 with a palm or a finger. In addition, by providing a backlight or a sensing light source emitting near-infrared light to the display unit, an image of a finger vein or a palm vein can be taken.

In addition, the configuration shown in the present embodiment can be appropriately combined with any of the configurations of the first to fourth embodiments.

As described above, since the application range of the light-emitting device including the light-emitting element described in Embodiment 1 is wide, the light-emitting device can be applied to electronic devices in various fields. By using the light-emitting element described in Embodiment 1, an electronic device with high reliability can be obtained.

8 shows an example of a liquid crystal display device in which the light-emitting element described in Embodiment 1 is used for a backlight. The liquid crystal display device illustrated in FIG. 8 includes a housing 901, a liquid crystal layer 902, a backlight unit 903, and a housing 904. The liquid crystal layer 902 is connected to the driver IC 905. The light-emitting element described in Embodiment 1 is used in the backlight unit 903, and a current is supplied through the terminal 906.

By using the light-emitting element described in Embodiment 1 for a backlight of a liquid crystal display device, a backlight with low power consumption can be obtained. Further, by using the light emitting device described in Embodiment 1, it is possible to manufacture a surface-emitting lighting device and a large-area surface-emitting lighting device, so that the backlight can be used as a large-area backlight, and the liquid crystal display device is also a large-area device. It can be done with. In addition, the light-emitting device including the light-emitting element described in Embodiment 1 can be thinner than the conventional device, and the display device can be thinner.

9 shows an example in which the light-emitting element described in Embodiment 1 is used for a table lamp that is a lighting device. The table lamp shown in FIG. 9 includes a housing 2001 and a light source 2002, and the lighting device described in the fourth embodiment may be used for the light source 2002.

10 shows an example in which the light-emitting element described in Embodiment 1 is used for the indoor lighting device 3001. Since the light-emitting element described in Embodiment 1 has high reliability, it can be set as a highly reliable lighting device. Further, since the light-emitting element described in Embodiment 1 can have a large area, the light-emitting element can be used for a large-area lighting device. In addition, since the light-emitting element described in Embodiment 1 is thin, the light-emitting element can be used in a lighting device having a reduced thickness.

The light-emitting element described in Embodiment 1 may be used for a windshield of a vehicle or a dashboard of a vehicle. Fig. 11 shows an embodiment in which the light-emitting element described in Embodiment 1 is used for a windshield of a vehicle and a dashboard of a vehicle. The display areas 5000 to 5005 each include the light emitting elements described in the first embodiment.

The display area 5000 and the display area 5001 are provided on a windshield of an automobile, and are display devices in which the light emitting elements described in the first embodiment are incorporated. The light-emitting element described in Embodiment 1 includes an anode and a cathode formed of an electrode having light-transmitting properties, so that a so-called see-through display device capable of viewing the opposite side can be obtained. Such a see-through display device can be provided to the windshield of an automobile without disturbing the visibility. Further, when a driving transistor or the like is provided, it is preferable to use a transistor having transmittance, such as an organic transistor using an organic semiconductor material or a transistor using an oxide semiconductor.

The display area 5002 is provided in a pillar portion, and is a display device in which the light emitting element described in the first embodiment is incorporated. The display area 5002 displays an image obtained by an imaging unit provided on the vehicle body, thereby supplementing the field of view covered by the filler. Similarly, the display area 5003 provided on the dashboard displays an image obtained by an imaging unit provided outside the vehicle body, thereby supplementing the field of view covered by the vehicle body, thereby eliminating a visual zone and enhancing safety. By displaying an image to compensate for an area that the driver cannot see, the driver can easily and comfortably check safety.

The display area 5004 and the display area 5005 may provide various types of information, such as navigation data, a speedometer, a tachometer, a driving distance, an oil supply amount, a shift gear status, and a setting of an air conditioner. The content or layout of the display can be appropriately changed freely by the user. In addition, such information can also be displayed by the display areas 5000 to 5003. The display areas 5000 to 5005 may be used as a lighting device.

12A and 12B illustrate an example of a foldable tablet terminal. Figure 12 (A) shows the unfolded tablet terminal. The tablet terminal includes a housing 9630, a display portion 9631a, a display portion 9631b, a display mode switch 9034, a power switch 9035, a power saving mode switch 9036, a clasp 9033, and operation. And a switch 9038. In addition, in the tablet terminal, one or both of the display portion 9631a and the display portion 9631b are formed using the light emitting device including the light emitting element described in the first embodiment.

A part of the display unit 9631a may be the touch screen area 9632a, and data may be input by touching the displayed operation key 9637. Although half of the display portion 9631a has only a display function and the other half has a touch screen function, one embodiment of the present invention is not limited to this configuration. The entire display portion 9631a may have a touch screen function. For example, a keyboard can be displayed on the entire area of the display portion 9631a so that the display portion 9631a is used as a touch screen, and the display portion 9631b can be used as a display screen.

Like the display portion 9631a, a part of the display portion 9631b may be used as the touch screen area 9632b. When the switch button 9639 for displaying or hiding the keyboard on the touch screen is touched with a finger or a stylus, the keyboard may be displayed on the display unit 9631b.

A touch input may be simultaneously performed in the touch screen area 9632a and the touch screen area 9632b.

The display mode switch 9034 can switch the display between, for example, a portrait mode and a landscape mode, and between a black and white display and a color display. The power saving mode switch 9036 may control display luminance according to the amount of external light when using the tablet terminal, which is detected by an optical sensor built into the tablet terminal. In addition to the optical sensor, another detection device including a sensor such as a gyroscope or an acceleration sensor for detecting the inclination may be incorporated in the tablet terminal.

12A shows an example in which the display portion 9631a and the display portion 9631b have the same display area, but one embodiment of the present invention is not limited to this example. The display area and display quality of the display portion 9631a and the display portion 9631b may be different. For example, an image with a higher resolution may be displayed on one of the display portions 9631a and 9631b.

Figure 12 (B) shows a folded tablet terminal. The tablet terminal of the present embodiment includes a housing 9630, a solar cell 9633, a charge/discharge control circuit 9634, a battery 9635, and a DCDC converter 9636. In FIG. 12B, a configuration including a battery 9535 and a DCDC converter 9636 is shown as an example of the charge/discharge control circuit 9634.

Since the tablet terminal is foldable, the housing 9630 can be closed when the tablet terminal is not in use. As a result, since the display portion 9631a and the display portion 9631b can be protected, a tablet terminal having high durability and high reliability for long-term use can be provided.

The tablet terminal shown in FIGS. 12A and 12B is a function of displaying various data (eg, still images, moving pictures, and text images), a function of displaying a calendar, a date, or a time on the display unit. , A touch input function of manipulating or editing data displayed on the display unit by a touch input, and a function of controlling processing by various software (programs).

The solar cell 9633 provided on the surface of the tablet terminal may supply power to a touch screen, a display unit, or a video signal processing unit. In addition, a structure in which the solar cells 9633 are provided on one or both sides of the housing 9630 is preferable because the battery 9635 can be efficiently charged.

The structure and operation of the charge/discharge control circuit 9634 shown in FIG. 12B will be described with reference to the block diagram of FIG. 12C. 12C shows a solar cell 9633, a battery 9635, a DCDC converter 9636, a converter 9638, switches SW1 to SW3, and a display portion 9631. The battery 9635, the DCDC converter 9636, the converter 9638, and the switches SW1 to SW3 correspond to the charge/discharge control circuit 9634 shown in Fig. 12B.

First, an example of an operation when electric power is generated by the solar cell 9633 using external light will be described. The voltage of the electric power generated by the solar cell is raised or lowered by the DCDC converter 9636 to become a voltage for charging the battery 9635. And, when the power from the solar cell 9633 is used for the operation of the display unit 9631, the switch SW1 is turned on, and the voltage of the power is increased by the converter 9638 so that the voltage required for the display unit 9631 is set. Or descend. When an image is not displayed on the display portion 9631, the switch SW1 is turned off and the switch SW2 is turned on to charge the battery 9635.

Although the solar cell 9633 has been described as an example of the power generating means, the power generating means is not particularly limited, and the battery 9635 may be charged by other power generating means such as a piezoelectric element or a thermoelectric conversion element (Peltier element). good. The battery 9635 may be charged by a combination of a non-contact power transmission module capable of transmitting and receiving power by wireless (non-contact) and charging, or any of other charging means, and no power generation means need to be provided.

As long as the display portion 9631 is included, one embodiment of the present invention is not limited to a tablet terminal having a shape shown in FIGS. 12A to 12C.

13A to 13C illustrate a foldable portable information terminal 9310. 13A shows the open portable information terminal 9310. 13B shows the portable information terminal 9310 which is unfolded or folded. 13C shows the folded portable information terminal 9310. When the portable information terminal 9310 is folded, portability is high. When the portable information terminal 9310 is unfolded, there is no seam and a large display area provides high visibility.

The display panel 9311 is supported by three housings 9315 connected to each other by hinges 9313. The display panel 9311 may be a touch panel (input/output device) including a touch sensor (input device). By bending the display panel 9311 using the hinge 9313 at the connection between the two housings 9315, the portable information terminal 9310 can be reversibly transformed from an open state to a folded state. The light emitting device of one embodiment of the present invention can be used for the display panel 9311. The display area 9312 of the display panel 9311 includes a display area located on the side of the folded portable information terminal 9310. In the display area 9312, an information icon, an application with a high frequency of use, and a shortcut to a program can be displayed, and information can be checked and an application can be started smoothly.

In addition, an organic compound having a substituted or unsubstituted benzonaphthofuran skeleton and one substituted or unsubstituted amine skeleton, which is one embodiment of the present invention, can be used in an organic thin film solar cell. More specifically, since the compound has carrier transport properties, it can be used for a carrier transport layer or a carrier injection layer. In addition, a mixed film of the compound and an upceptor material may be used as the charge generation layer. In addition, the compound can be photo-excited, and thus can be used in a power generation layer.

(Example 1)

<<Synthesis Example 1>>

In this synthesis example, the organic compound of one embodiment of the present invention represented by the structural formula (142) in the embodiment, N- (4-biphenyl)-6, N -diphenylbenzo[ b ]naphtho[1,2- d ]Furan-8-amine (abbreviation: BnfABP) is shown in detail the synthesis example. The structural formula of BnfABP is as follows.

[Chemical Formula 56]

<Step 1: Synthesis of 6-iodobenzo[ b ]naphtho[1,2- d ]furan>

8.5 g (39 mmol) of benzo[ b ]naphtho[1,2- d ]furan was added to a 500 mL three-necked flask, and air in the flask was replaced with nitrogen. Then, 195 mL of tetrahydrofuran (THF) was added thereto. After cooling this solution to -75°C, 25 mL (40 mmol) of n -butyllithium (1.59 mol/L n -hexane solution) was added dropwise to the solution. After dropping, the resulting solution was stirred at room temperature for 1 hour. After a certain time, the resulting solution was cooled to -75°C. Then, a solution in which 10 g (40 mmol) of iodine was dissolved in 40 mL of THF was added dropwise to this solution. After dropping, this solution was stirred for 17 hours while returning the temperature of the resulting solution to room temperature. Next, an aqueous solution of sodium thiosulfate was added to the mixture, and the resulting mixture was stirred for 1 hour. Then, the organic layer of the mixture was washed with water and dried over magnesium sulfate. After drying, the mixture was subjected to gravity filtration to obtain a solution. The resulting solution was filtered with suction through Florisil (manufactured by Wako Pure Chemical Industries, Ltd., catalog number 066-05265) and Celite (manufactured by Wako Pure Chemical Industries, Ltd., catalog number 537-02305) to obtain a filtrate. Got it. The resulting filtrate was concentrated to obtain a solid. The resulting solid was recrystallized from toluene to obtain 6.0 g (18 mmol) of the target white powder in a yield of 45%. The synthesis scheme (a-1) of step 1 is shown below.

[Chemical Formula 57]

<Step 2: Synthesis of 6-phenylbenzo[ b ]naphtho[1,2- d ]furan>

In a 200 mL three-necked flask, 6.0 g (18 mmol) of 6-iodobenzo[ b ]naphtho[1,2- d ]furan, 2.4 g (19 mmol) of phenylboronic acid, 70 mL of toluene, 20 mL of ethanol, and 22 mL of potassium carbonate aqueous solution (2.0 mol/L) was added. The mixture was degassed by stirring while lowering the pressure. After degassing, air in the flask was replaced with nitrogen, and then 480 mg (0.42 mmol) of tetrakis(triphenylphosphine)palladium(0) was added to the mixture. The resulting mixture was stirred at 90° C. for 12 hours under a stream of nitrogen. After a predetermined time, water was added to this mixture, and extraction with toluene was performed in the aqueous layer. The extracted solution and the organic layer were mixed, and the mixture was washed with water, and then dried over magnesium sulfate. This mixture was subjected to gravity filtration to obtain a filtrate. The resulting filtrate was concentrated to obtain a solid, and the resulting solid was dissolved in toluene. The resulting solution was aspirated through Celite (manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), Florisil (manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 540-00135), and alumina. Filtration was performed to obtain a filtrate. The resulting filtrate was concentrated to obtain a solid. The resulting solid was recrystallized from toluene to obtain 4.9 g (17 mmol) of the target white solid in a yield of 93%. The synthesis scheme (b-1) of step 2 is shown below.

[Chemical Formula 58]

<Step 3: Synthesis of 8-iodo-6-phenylbenzo[ b ]naphtho[1,2, d ]furan>

In a 300 mL three-necked flask, 4.9 g (17 mmol) of 6-phenylbenzo[ b ]naphtho[1,2- d ]furan was placed, and air in the flask was replaced with nitrogen. Then, 87 mL of tetrahydrofuran (THF) was added thereto. The resulting solution was cooled to -75°C. Then, 11 mL (18 mmol) of n -butyllithium (1.59 mol/L n -hexane solution) was added dropwise to this solution. After dropping, the resulting solution was stirred at room temperature for 1 hour. After a certain time, the resulting solution was cooled to -75°C. Then, to the resulting solution, a solution in which 4.6 g (18 mmol) of iodine was dissolved in 18 mL of THF was added dropwise. This solution was stirred for 17 hours while returning the temperature of the resulting solution to room temperature. After stirring, an aqueous solution of sodium thiosulfate was added to the mixture, and the resulting mixture was stirred for 1 hour. Then, the organic layer of the mixture was washed with water and dried over magnesium sulfate. This mixture was subjected to gravity filtration to obtain a filtrate. The resulting filtrate was passed through Celite (manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), Florisil (manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 540-00135), and alumina. Filtrate was obtained by suction filtration. The resulting filtrate was concentrated to obtain a solid. The resulting solid was recrystallized from toluene to obtain 3.7 g (8.8 mmol) of the target white solid in a yield of 53%. The synthesis scheme (c-1) of step 3 is shown below.

[Chemical Formula 59]

<Step 4: Synthesis of 6, N -diphenylbenzo[ b ]naphtho[1,2- d ]furan-8-amine>

In a 200 mL three necked flask, 5.0 g (12 mmol) of 8-iodo-6-phenylbenzo[ b ]naphtho[1,2- d ]furan and 2.9 g (30 mmol) of sodium tert -butoxide synthesized in step 3 Side was added. The air in the flask was replaced with nitrogen. Then, 60 mL of toluene, 1.4 g (13 mmol) of aniline, and 0.4 mL of tri( tert -butyl)phosphine (10 wt% hexane solution) were added. After degassing the mixture under reduced pressure, the temperature was set to 60°C under a stream of nitrogen, and 60 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium (0) was added, and the mixture was added at 60°C to 40°C. Stir for a minute. After stirring, the obtained mixture was washed with water and a saturated aqueous solution of sodium chloride, and the organic layer was dried over magnesium sulfate. After removing magnesium sulfate by gravity filtration, the obtained filtrate was concentrated to obtain a white solid. This solid was purified by silica gel column chromatography (developing solvent is a mixed solvent of toluene:hexane = 1:2) to obtain 3.5 g of the target white solid in a yield of 77%. The synthesis scheme (d-1) of step 4 is shown below.

[Chemical Formula 60]

^{The 1} H NMR data of the obtained white solid are shown below.

¹ H NMR (chloroform-d,500MHz): δ=6.23(s,1H), 7.04(t,J=7.5Hz,1H), 7.24-7.26(m,2H), 7.34-7.41(m,4H) , 7.47(t,J=8.0Hz,1H), 7.54-7.60(m,3H), 7.74(t,J=7.5Hz,1H), 7.95(d,J=6.5Hz,2H), 7.99(dd, J1=1.5Hz, J2=7.0Hz,1H), 8.03(s,1H), 8.08(d,J=8.0Hz,1H), 8.66(d,J=9.0Hz,1H)

<Step 5: Synthesis of N -4-biphenyl-6, N -diphenylbenzo[ b ]naphtho[1,2- d ]furan-8-amine>

In a 200 mL 3-neck flask, 1.3 g (5.0 mmol) of 4-bromobiphenyl, 1.9 g (5.0 mmol) of 6, N -diphenylbenzo[ b ]naphtho[1,2- d ] synthesized in step 4 Furan-8-amine, 0.14 g (0.30 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (abbreviation: X-Phos), and 1.5 g (15 mmol) of Sodium tert -butoxide was added. After the air in the flask was replaced with nitrogen, 25 mL of toluene was added. After degassing the mixture under reduced pressure, the temperature was set to 60°C under a flow of nitrogen, and 61 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium (0) was added, and the mixture was 3 at 80°C. Stir for hours. After stirring, the obtained mixture was washed with water and a saturated aqueous solution of sodium chloride, and the organic layer was dried over magnesium sulfate. After removing magnesium sulfate by gravity filtration, the obtained filtrate was concentrated to obtain a brown solid. This solid was purified by silica gel column chromatography (developing solvent is a mixed solvent of toluene:hexane = 3:7) to obtain 2.0 g of the target pale yellow solid in a yield of 67%. The synthesis scheme (e-1) of step 5 is shown below.

[Chemical Formula 61]

^{The 1} H NMR data of the obtained pale yellow solid are shown below. 14A and 14B are ¹ H NMR charts. In addition, FIG. 14B is a chart showing an enlarged portion of the range of 7.00ppm to 9.00ppm in FIG. 14A. These results show that BnfABP, which is an organic compound of one embodiment of the present invention, was obtained.

¹ H NMR (dichloromethane-d2, 500MHz): δ=7.11(t,J=7.0Hz,1H), 7.16(t,J=7.0Hz,4H), 7.22-7.33(m,7H), 7.39 -7.47(m,5H), 7.53-7.60(m,5H), 7.74(t,J=7.0Hz,1H), 8.02(s,1H), 8.06(d,J=8.0Hz,1H), 8.23( d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H)

1.5 g of the light yellow solid obtained was purified by train sublimation. Purification by sublimation was performed under a pressure of 3.6 Pa, at a flow rate of 15 mL/min of argon gas, at a temperature of 235°C to 250°C for 16 hours. After purification by sublimation, 1.4 g of the target pale yellow solid was obtained with a recovery rate of 90%.

Next, the ultraviolet-visible absorption spectrum (hereinafter simply referred to as "absorption spectrum") and emission spectrum of the toluene solution of BnfABP and the solid thin film were measured. A solid thin film was formed on the quartz substrate by vacuum evaporation. The absorption spectrum of the toluene solution was measured using an ultraviolet visible light spectrophotometer (type V550, manufactured by JASCO Corporation), and the spectrum of only toluene placed in a quartz cell was subtracted from the measured spectrum. The absorption spectrum of the thin film was measured using a spectrophotometer (U-4100 spectrophotometer, manufactured by Hitachi High-Technologies Corporation). The emission spectrum was measured using a fluorescence spectrophotometer (FS920, manufactured by Hamamatsu Photonics K.K.). Fig. 15 shows the measurement results of the absorption and emission spectra of the obtained toluene solution, and Fig. 16 shows the measurement results of the absorption and emission spectra of the obtained thin film.

From Fig. 15, the toluene solution of BnfABP has absorption peaks around 376 nm, 340 nm, and 321 nm, and emission peaks at 417 nm (excitation wavelength: 370 nm).

From Fig. 16, the thin film of BnfABP has absorption peaks around 387 nm, 346 nm, 326 nm, 294 nm, and 262 nm, and emission peaks at 440 nm (excitation wavelength: 360 nm).

The HOMO level and the LUMO level of BnfABP were obtained through cyclic voltammetry (CV) measurement. The calculation method will be described below.

As a measuring device, an electrochemical analyzer (ALS model 600A or 600C, manufactured by BAS Inc.) was used. As a solution used for CV measurement, dehydrated dimethylformamide (DMF, product of Sigma-Aldrich Inc., 99.8%, catalog number 22705-6) was used as a solvent, and tetra- n -butylammonium perchlorate as a supporting electrolyte ( n -Bu ₄ NClO ₄ , a product of Tokyo Chemical Industry Co., Ltd., catalog number T0836) was dissolved in a solvent so that the concentration of tetra-n-butylammonium perchlorate was 100 mmol/L. Further, the measurement object was also dissolved in a solvent so that the concentration was 2 mmol/L. A platinum electrode (PTE platinum electrode, manufactured by BAS Inc.) was used as the working electrode, another platinum electrode (Pt counter electrode for VC-3 (5 cm), manufactured by BAS Inc.) was used as the auxiliary electrode, and Ag as a reference electrode. /Ag ⁺ electrode (RE7 reference electrode for non-aqueous solvent, manufactured by BAS Inc.) was used. In addition, the measurement was performed at room temperature (20°C to 25°C). In addition, the scan rate at the time of CV measurement was 0.1 V/sec, and the oxidation potential Ea[V] and reduction potential Ec[V] with respect to the reference electrode were measured. The potential Ea is the intermediate potential of the redox wave, and Ec is the intermediate potential of the reduction-oxidation wave. Here, since it is known that the potential energy for the vacuum level of the reference electrode used in this embodiment is -4.94 [eV], the HOMO level and the LUMO level can be obtained from the following equation: HOMO level [eV]=- 4.94-Ea and LUMO level [eV]=-4.94-Ec. Further, the CV measurement was repeated 100 times, and the electrical stability of the compound was investigated by comparing the oxidation-reduction wave at the 100th cycle and the oxidation-reduction wave at the 1st cycle.

As a result, it was found that the HOMO level of BnfABP was -5.59 eV, and its LUMO level was -2.53 eV. After the 100th cycle, the peak intensity of the oxidation-reduction wave was maintained at 83% of the peak intensity of the oxidation-reduction wave of the first cycle, indicating that BnfABP has excellent resistance to oxidation. Thermal gravimetric differential thermal analysis (TG/DTA) of BnfABP was performed. This measurement was performed using a high vacuum differential differential thermal balance (TG-DTA 2410SA, manufactured by Bruker AXS K.K.). This measurement was carried out under a nitrogen stream (flow rate: 200 mL/min), at normal pressure, at a temperature increase rate of 10°C/min. From the relationship between weight and temperature (thermogravimetric measurement), the 5% weight loss temperature of BnfABP was about 370°C. This indicates that the heat resistance of BnfABP is high. In addition, differential scanning calorimetry (DSC measurement) was performed by Pyris1DSC manufactured by PerkinElmer, Inc. In differential scanning calorimetry, after raising the temperature from -10°C to 300°C at a heating rate of 40°C/min, maintaining this temperature for 1 minute, then cooling to -10°C at a rate of 40°C/min. Made it. This operation was repeated twice in succession. From the DSC measurement, it was found that the glass transition temperature of BnfABP was 97°C, and thus the heat resistance was high.

(Example 2)

<<Synthesis Example 2>>

In this synthesis example, the organic compound of one embodiment of the present invention represented by the structural formula (146) in the embodiment, N , N -bis(biphenyl-4-yl)-6-phenylbenzo[ b ]naphtho[1, It shows the synthesis example of 2- d ]furan-8-amine (abbreviation: BBABnf). The structural formula of BBABnf is as follows.

[Formula 62]

<Step 1: Synthesis of 6-iodobenzo[ b ]naphtho[1,2- d ]furan>

This synthesis step is the same as Step 1 of Synthesis Example 1.

<Step 2: Synthesis of 6-phenylbenzo[ b ]naphtho[1,2- d ]furan>

This synthesis step is the same as that of Step 2 in Synthesis Example 1.

<Step 3: Synthesis of 8-iodo-6-phenylbenzo[ b ]naphtho[1,2, d ]furan>

This synthesis step is the same as Step 3 of Synthesis Example 1.

<Step 4: (9,9-dimethyl-9 H -fluorene-2,7-diyl)bis(6, N -diphenylbenzo[ b ]naphtho[1,2- d ]furan-8- Synthesis of amine>

In a 200 mL three-necked flask, 2.1 g (5.0 mmol) of 8-iodo-6-phenylbenzo[ b ]naphtho[1,2- d ]furan obtained in step 3 of Example 1, 1.6 g (5.0 mmol) ) Of di(1,1'-biphenyl-4-yl)amine, 0.17 g (0.40 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (Abbreviation: S-Phos), and 0.97 g (10 mmol) of sodium tert -butoxide were added. After the air in the flask was replaced with nitrogen, 25 mL of xylene was added. After degassing the mixture under reduced pressure, the temperature was set to 80°C under a stream of nitrogen, and 0.12 g (0.20 mmol) of bis(dibenzylideneacetone)palladium (0) was added, and the mixture was added at 80°C. The mixture was stirred for 5.5 hours and further stirred at 100° C. for 5 hours. After stirring, the obtained mixture was washed with water and a saturated aqueous solution of sodium chloride, and the organic layer was dried over magnesium sulfate. After removing magnesium sulfate by gravity filtration, the obtained filtrate was concentrated to obtain a brown solid. The obtained solid was dissolved in toluene, and filtered through celite (manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 537-02305) and alumina. The obtained filtrate was concentrated to obtain 2.0 g of the target yellow solid in a yield of 67%. The synthesis scheme (d-2) of step 4 is shown below.

[Chemical Formula 63]

^{The 1} H NMR data of the obtained yellow solid are shown below. 17A and 17B are ¹ H NMR charts. In addition, FIG. 17B is a chart showing an enlarged portion of the range of 7.00ppm to 9.00ppm in FIG. 17A. These results show that BBABnf, which is an organic compound of one embodiment of the present invention, was obtained.

¹ H NMR (dichloromethane-d2, 500MHz): δ=7.14-7.19(m,3H), 7.22(d,J=8.5Hz,4H), 7.29-7.33(m,3H), 7.41(t, J=8.0Hz,4H), 7.44-7.49(m,3H), 7.55-7.58(m, 5H), 7.61(d,J=8.0Hz,4H), 7.74(t,J=8.0Hz,1H), 8.02(s,1H), 8.06(d,J=8.0Hz,1H), 8.26(d,1H), 8.67(d,J=8.0Hz,1H)

2.0 g of the obtained yellow solid was purified by train sublimation. Purification by sublimation was performed under a pressure of 3.8 Pa, at a flow rate of 15 mL/min of argon gas, at a temperature of 270° C., for 16 hours. After purification by sublimation, 1.7 g of the target yellow solid was obtained with a yield of 81%.

Next, the ultraviolet-visible absorption spectrum (hereinafter simply referred to as "absorption spectrum") and emission spectrum of the toluene solution of BBABnf and the solid thin film were measured. The measurement was carried out with an apparatus and method similar to that of BnfABP. Fig. 18 shows the measurement results of absorption and emission spectra of the obtained toluene solution, and Fig. 19 shows the measurement results of absorption and emission spectra of the obtained thin film.

From Fig. 18, the toluene solution of BBABnf has an absorption peak around 343 nm, and light emission has a peak at 420 nm (excitation wavelength: 340 nm).

From Fig. 19, the thin film of BBABnf has absorption peaks around 344 nm, 325 nm, and 257 nm, and emission peaks at 439 nm (excitation wavelength: 361 nm).

The HOMO level and LUMO level of BBABnf were obtained through cyclic voltammetry (CV) measurement. The calculation method is similar to that described in Example 1.

As a result, it was found that the HOMO level of BBABnf was -5.56 eV, and its LUMO level was -2.51 eV. After the 100th cycle, the peak intensity of the oxidation-reduction wave was maintained at 90% of the peak intensity of the oxidation-reduction wave of the first cycle, indicating that BBABnf has excellent resistance to oxidation. TG-DTA and DSC measurements of BBABnf were performed in a similar manner to that of BnfABP. In addition, in DSC measurement, the temperature was raised to 330°C. From the TG-DTA measurement, the 5% weight loss temperature of BBABnf was about 410°C. This indicates that the heat resistance of BBABnf is high. From the DSC measurement, it was found that the glass transition temperature of BBABnf was 117°C, so that the heat resistance was high.

(Example 3)

In this example, the light-emitting element 1 of one embodiment of the present invention described in the first embodiment will be described. The structural formula of the organic compound used in Light-Emitting Element 1 is shown below.

[Formula 64]

(Method of manufacturing light-emitting element 1)

First, on a glass substrate, a film of indium tin oxide (ITSO) containing silicon oxide was formed by sputtering to form an anode 101. The thickness was set to 70 nm, and the electrode area was set to 2 mm×2 mm.

Next, as a pretreatment for forming a light emitting device on the substrate, the surface of the substrate was washed with water and fired at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.

Thereafter, the ^{substrate was moved to a vacuum evaporation apparatus having a pressure reduced to about 10 -4} Pa, and vacuum firing was performed at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled for about 30 minutes. .

Next, the substrate provided with the anode 101 was fixed to the substrate holder provided in the vacuum evaporation apparatus so that the side on which the anode 101 was formed was facing downward. And, on the anode 101, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene represented by the structural formula (i) (abbreviation : HAT-CN) was deposited to a thickness of 5 nm by a deposition method using resistance heating to form a hole injection layer 111.

Next, N- (1,1'-biphenyl-4-yl)-9,9-dimethyl- N- [4-(9-panyl-9 H -carbazole-3) represented by structural formula (ii) -yl) phenyl] -9 H-fluorene-2-amine pullulans (abbreviation: PCBBiF) the deposition of a hole injecting layer 111, 25nm thickness by vapor deposition on and represented by the following structural formula (iii) N, N-bis ( Biphenyl-4-yl)-6-phenylbenzo[ b ]naphtho[1,2- d ]furan-8-amine (abbreviation: BBABnf) was deposited to a thickness of 5 nm by evaporation to form the hole transport layer 112 Formed.

Then, 7- [4- (10-phenyl-9-anthryl) phenyl] represented by the following structural formula (iv) -7 H - dibenzo [c, g] carbazole (abbreviation: cgDBCzPA) and formula (v) represented by N, N '- bis (3-methylphenyl) - N, N' - bis [4- (9-phenyl -9 H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (Abbreviation: 1,6mMemFLPAPrn) was co-deposited at a weight ratio of 1:0.03 (=cgDBCzPA: 1,6mMemFLPAPrn) to a thickness of 25 nm to form the light emitting layer 113.

Then, on the light emitting layer 113, cgDBCzPA was deposited to a thickness of 10 nm by evaporation, and vasophenanthroline (abbreviation: BPhen) represented by structural formula (vi) was deposited to a thickness of 15 nm by evaporation, thereby forming the electron transport layer 114 Formed.

After the electron transport layer 114 was formed, lithium fluoride (LiF) was deposited to a thickness of 1 nm by vapor deposition to form the electron injection layer 115. Then, the cathode 102 was formed by depositing aluminum to a thickness of 200 nm by evaporation. Thus, Light-Emitting Element 1 of this Example was fabricated.

The device structure of Light-Emitting Element 1 is shown in the following table.

Light-emitting element 1 was sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the atmosphere (specifically, a sealing material was applied to surround the element, and UV treatment and at 80°C during sealing. 1 hour of heat treatment was performed). Then, the initial characteristics and reliability of this light-emitting device were measured. In addition, this measurement was carried out at room temperature (atmosphere maintained at 25°C).

20 shows the luminance-current density characteristics of Light-Emitting Element 1. 21 shows current efficiency-luminance characteristics of Light-Emitting Element 1. 22 shows the luminance-voltage characteristics of Light-Emitting Element 1. 23 shows current-voltage characteristics of Light-Emitting Element 1. 24 shows external quantum efficiency-luminance characteristics of Light-Emitting Element 1. 25 shows an emission spectrum of Light-Emitting Element 1. Table 2 shows the main characteristics of Light-Emitting Element 1 in the vicinity of 1000 cd/m ^2.

From FIGS. 20 to 25 and Table 2, it was found that the light emitting device 1 of one embodiment of the present invention is a blue light emitting device having good efficiency and low driving voltage.

26 shows the driving time-dependent change of the luminance of the light-emitting element under the condition that the current value is set to 2 mA and the current density is constant. As shown in Fig. 26, it was found that the light-emitting element is a light-emitting element having a long life with a small decrease in luminance according to the driving time.

(Example 4)

In this example, the light-emitting elements 2 and 3 of one embodiment of the present invention described in the first embodiment will be described. Structural formulas of the organic compounds used in Light-Emitting Elements 2 and 3 are shown below.

[Formula 65]

(Method of manufacturing light-emitting element 2)

First, on a glass substrate, a film of indium tin oxide (ITSO) containing silicon oxide was formed by sputtering to form an anode 101. The thickness was set to 70 nm, and the electrode area was set to 2 mm×2 mm.

Next, as a pretreatment for forming a light emitting device on the substrate, the surface of the substrate was washed with water and fired at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.

Thereafter, the ^{substrate was moved to a vacuum evaporation apparatus having a pressure reduced to about 10 -4} Pa, and vacuum firing was performed at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled for about 30 minutes. .

Next, the substrate provided with the anode 101 was fixed to the substrate holder provided in the vacuum evaporation apparatus so that the side on which the anode 101 was formed was facing downward. And, on the anode 101, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene represented by the structural formula (i) (abbreviation : HAT-CN) was deposited to a thickness of 5 nm by a deposition method using resistance heating to form a hole injection layer 111.

Next, on the hole injection layer 111, N- (1,1'-biphenyl-4-yl)-9,9-dimethyl- N- [4-(9-phenyl) represented by the structural formula (ii) -9 H - carbazol-3-yl) phenyl] -9 H - fluorene-2-amine (abbreviation: by depositing a thickness of 20nm by a PCBBiF) to the deposition and formation of the first hole transport layer (112-1); On the first hole transport layer 112-1, N , N -bis(biphenyl-4-yl)-6-phenylbenzo[ b ]naphtho[1,2- d ]furan- represented by the structural formula (iii) 8-amine (abbreviation: BBABnf) was deposited to a thickness of 5 nm by vapor deposition to form the second hole transport layer 112-2; 2 on the hole transport layer (112-2), formula (vii) 3- [4- (9- phenanthryl) -phenyl] -9-phenyl represented by -9 H-carbazole (abbreviation: PCPPn) to the evaporation As a result, the third hole transport layer 112-3 was formed by depositing to a thickness of 5 nm.

Then, 7- [4- (10-phenyl-9-anthryl) phenyl] represented by the following structural formula (iv) -7 H - dibenzo [c, g] carbazole (abbreviation: cgDBCzPA) and formula (v) represented by N, N '- bis (3-methylphenyl) - N, N' - bis [4- (9-phenyl -9 H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (Abbreviation: 1,6mMemFLPAPrn) was co-deposited at a weight ratio of 1:0.03 (=cgDBCzPA: 1,6mMemFLPAPrn) to a thickness of 25 nm to form the light emitting layer 113.

Then, on the light emitting layer 113, cgDBCzPA was deposited to a thickness of 10 nm by evaporation, and vasophenanthroline (abbreviation: BPhen) represented by structural formula (vi) was deposited to a thickness of 15 nm by evaporation, thereby forming the electron transport layer 114 Formed.

After the electron transport layer 114 was formed, lithium fluoride (LiF) was deposited to a thickness of 1 nm by vapor deposition to form the electron injection layer 115. Then, the cathode 102 was formed by depositing aluminum to a thickness of 200 nm by evaporation. As a result, light-emitting element 2 of this example was fabricated.

(Method of manufacturing light-emitting element 3)

Light-emitting element 3, in place of the second hole transport layer (112-2) BBABnf N- (4-biphenyl)-6, N -diphenylbenzo[ b ]naphtho[1,2- d ]furan-8- It was formed in the same manner as Light-Emitting Element 2, except that it was formed using an amine (abbreviation: BnfABP).

The device structures of Light-Emitting Elements 2 and 3 are shown in the following table.

Light-emitting elements 2 and 3 were sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the atmosphere (specifically, a sealing material was applied to surround the element, and UV treatment and 80 1 hour of heat treatment at °C was performed). Then, the initial characteristics and reliability of this light-emitting device were measured. In addition, this measurement was carried out at room temperature (atmosphere maintained at 25°C).

27 shows the luminance-current density characteristics of Light-Emitting Elements 2 and 3; 28 shows current efficiency-luminance characteristics of Light-Emitting Elements 2 and 3; 29 shows the luminance-voltage characteristics of Light-Emitting Elements 2 and 3; 30 shows current-voltage characteristics of Light-Emitting Elements 2 and 3; 31 shows external quantum efficiency-luminance characteristics of Light-Emitting Elements 2 and 3; 32 shows emission spectra of Light-Emitting Elements 2 and 3. Table 4 shows the main characteristics of Light-Emitting Elements 2 and 3 in the vicinity of 1000 cd/m ^2.

27 to 32 and Table 4, it was found that the light emitting devices 2 and 3 of one embodiment of the present invention are blue light emitting devices having good efficiency and low driving voltage.

33 shows the driving time-dependent change of the luminance of the light-emitting element under the condition that the current value is set to 2 mA and the current density is constant. As shown in FIG. 33, it was found that the light-emitting elements 2 and 3 maintained at least 94% of the initial luminance after driving for 40 hours and had a very small reduction in luminance according to the driving time, and were long-lived light-emitting devices.

(Example 5)

<<Synthesis Example 3>>

In this synthesis example, N , N -bis(4-biphenyl)benzo[ b ]naphtho[1,2- d ]furan-, which is an organic compound of one embodiment of the present invention represented by the structural formula (229) in the embodiment. It shows the synthesis example of 6-amine (abbreviation: BBABnf(6)). The structural formula of BBABnf(6) is as follows.

[Formula 66]

<Step 1: Synthesis of 6-iodobenzo[ b ]naphtho[1,2- d ]furan>

The synthesis step of 6-iodobenzo[ b ]naphtho[1,2- d ]furan is similar to step 1 in Synthesis Example 1 of Example 1.

<Step 2: Synthesis of BBABnf(6)>

In a 200 mL three-necked flask, 2.7 g (8.0 mmol) of 6-iodobenzo[ b ]naphtho[1,2- d ]furan obtained in step 1, 2.6 g (8.0 mmol) of bis(1,1') -Biphenyl-4-yl)amine, 0.19 g (0.40 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (abbreviation: X-Phos), and 1.5 g (15 mmol) of sodium tert -butoxide was added. After the air in the flask was replaced with nitrogen, 40 mL of xylene was added. After degassing the mixture under reduced pressure, the temperature was set to 80°C under a stream of nitrogen, and 0.11 g (0.20 mmol) of bis(dibenzylideneacetone)palladium (0) was added, and the mixture was added at 120°C. The mixture was stirred for 3 hours and further stirred at 140° C. for 6.5 hours. After stirring, the obtained mixture was washed with water and a saturated aqueous solution of sodium chloride, and the organic layer was dried over magnesium sulfate. After removing magnesium sulfate by gravity filtration, the obtained filtrate was concentrated to obtain a brown solid. The obtained solid was purified by high performance liquid chromatography (mobile phase: chloroform) to obtain 3.4 g of the target pale yellow solid in a yield of 79%. The synthesis scheme (d-3) of Step 2 is shown below.

[Chemical Formula 67]

^{The 1} H NMR data of the obtained pale yellow solid are shown below. 36A and ^{36B are 1} H NMR charts. In addition, FIG. 36B is a chart showing an enlarged portion of the range of 7.00ppm to 9.00ppm in FIG. 36A. These results indicate that BBABnf (6), which is an organic compound of one embodiment of the present invention, was obtained in this Synthesis Example.

¹ H NMR (chloroform-d,500MHz): δ=7.25(d,J=8.5Hz,4H), 7.31(t,J=7.5Hz,2H), 7.41-7.48(m,6H), 7.51-7.54 (m,6H), 7.60(d,J=8.0Hz,4H), 7.67(t,J=7.5Hz,1H), 7.73(s,1H), 7.88(d,J=8.0Hz,1H), 8.42 (d,J=7.0Hz,1H), 6.83(d,J=8.0Hz,1H)

3.4 g of the obtained pale yellow solid was purified by train sublimation. Purification by sublimation was carried out under a pressure of 3.8 Pa, at a flow rate of 15 mL/min of argon gas, at a temperature of 275° C., for 15 hours. After purification by sublimation, 3.0 g of the target yellow solid was obtained with a recovery rate of 87%.

Next, the ultraviolet-visible absorption spectrum (hereinafter simply referred to as "absorption spectrum") and emission spectrum of the toluene solution of BBABnf(6) and the solid thin film were measured. The measurement was carried out with an apparatus and method similar to the measurement of Example 1. Fig. 37 shows the measurement results of absorption and emission spectra of the obtained toluene solution, and Fig. 38 shows the measurement results of absorption and emission spectra of the obtained thin film.

From Fig. 37, the toluene solution of BBABnf(6) has an absorption peak around 382 nm, and light emission has a peak at 429 nm (excitation wavelength: 337 nm).

From Fig. 38, the thin film of BBABnf(6) has an absorption peak around 390 nm, and light emission has a peak at 453 nm (excitation wavelength: 390 nm).

(Example 6)

<<Synthesis Example 4>>

In this synthesis example, N , N -bis(4-biphenyl)benzo[ b ]naphtho[1,2- d ]furan-, which is an organic compound of one embodiment of the present invention represented by the structural formula (189) in the embodiment. It shows the synthesis example of 8-amine (abbreviation: BBABnf(8)). The structural formula of BBABnf(8) is as follows.

[Chemical Formula 68]

<Step 1: Synthesis of BBABnf(8)>

In a 200 mL 3-neck flask, 2.0 g (8.0 mmol) of 8-chlorobenzo[ b ]naphtho[1,2- d ]furan, 2.6 g (8.0 mmol) of bis(1,1'-biphenyl-4) -Yl)amine, 0.19 g (0.40 mmol) 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (abbreviation: X-Phos), and 1.5 g (15 mmol) sodium tert -butoxide was added. After the air in the flask was replaced with nitrogen, 40 mL of xylene was added. After degassing the mixture under reduced pressure, the temperature was set to 80°C under a stream of nitrogen, and 0.11 g (0.20 mmol) of bis(dibenzylideneacetone)palladium (0) was added, and the mixture was added at 120°C. The mixture was stirred for 3 hours and further stirred at 140° C. for 6.5 hours. After stirring, the obtained mixture was heated at 120° C., without cooling Celite (manufactured by Wako Pure Chemical Industries, Ltd., catalog number 537-02305), Florisil (manufactured by Wako Pure Chemical Industries, Ltd., catalog number 066-). 05265), and filtered through alumina. The resulting filtrate was concentrated to obtain a light brown solid. The obtained solid was purified by high performance liquid chromatography (mobile phase: chloroform) to obtain 2.9 g of the target pale yellow solid in a yield of 68%. The synthesis scheme (d-4) of step 1 is shown below.

[Chemical Formula 69]

^{The 1} H NMR data of the obtained pale yellow solid are shown below. 39A and 39B are ¹ H NMR charts. In addition, FIG. 39(B) is a chart showing an enlarged portion of the range of 7.00 ppm to 9.00 ppm in FIG. 39(A). These results show that BBABnf(8), which is an organic compound of one embodiment of the present invention, was obtained.

¹ H NMR (chloroform-d,500MHz): δ=7.23(d,J=8.5Hz,4H), 7.31(t,J=7.5Hz,2H), 7.36(d,J=8.0Hz,1H), 7.42(t,J=8.0Hz,4H), 7.47(d,J=8.0Hz,1H), 7.52(d,J=9.0Hz,4H), 7.56(t,J=7.5Hz,1H), 7.59- 7.61(m,5H), 7.74(t,J=8.5Hz,1H), 7.87(d,J=8.0Hz,1H), 8.01(d,J=8.0Hz,1H), 8.25(d,J=8.0 Hz,1H), 8.65(d,J=8.0Hz,1H)

3.9 g of the obtained pale yellow solid was purified by train sublimation. Purification by sublimation was carried out under a pressure of 3.8 Pa, at a flow rate of 15 mL/min of argon gas, at a temperature of 275° C., for 15 hours. After purification by sublimation, 2.1 g of the target yellow solid was obtained with a recovery rate of 72%.

Next, the ultraviolet-visible absorption spectrum (hereinafter simply referred to as "absorption spectrum") and emission spectrum of the toluene solution of BBABnf(8) and the solid thin film were measured. The measurement was carried out with an apparatus and method similar to the measurement of Example 1. Fig. 40 shows the measurement results of absorption and emission spectra of the obtained toluene solution, and Fig. 41 shows the measurement results of absorption and emission spectra of the obtained thin film.

From Fig. 40, the toluene solution of BBABnf(8) has an absorption peak around 337 nm, and light emission has a peak at 410 nm (excitation wavelength: 337 nm).

From Fig. 41, the thin film of BBABnf(8) has an absorption peak around 370 nm, and light emission has a peak at 431 nm (excitation wavelength: 358 nm).

(Example 7)

In this example, the light-emitting elements 4 and 5 of one embodiment of the present invention described in the first embodiment will be described. The structural formulas of the organic compounds used in Light-Emitting Elements 4 and 5 are shown below.

[Formula 70]

(Method of manufacturing light-emitting element 4)

First, on a glass substrate, a film of indium tin oxide (ITSO) containing silicon oxide was formed by sputtering to form an anode 101. The thickness was set to 70 nm, and the electrode area was set to 2 mm×2 mm.

Next, as a pretreatment for forming a light emitting device on the substrate, the surface of the substrate was washed with water and fired at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.

Thereafter, the ^{substrate was moved to a vacuum evaporation apparatus having a pressure reduced to about 10 -4} Pa, and vacuum firing was performed at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled for about 30 minutes. .

Next, the substrate provided with the anode 101 was fixed to the substrate holder provided in the vacuum evaporation apparatus so that the side on which the anode 101 was formed was facing downward. And, on the anode 101, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene represented by the structural formula (i) (abbreviation : HAT-CN) was deposited to a thickness of 5 nm by a deposition method using resistance heating to form a hole injection layer 111.

Next, on the hole injection layer 111, 4,4'-bis[ N- (1-naphthyl) -N -phenylamino]biphenyl (abbreviation: NPB) represented by the structural formula (ix) was deposited by evaporation. Depositing to a thickness of 10 nm to form the first hole transport layer 112-1; On the first hole transport layer 112-1, N , N -di(4-biphenyl)benzo[ b ]naphtho[1,2-, which is an organic compound of one embodiment of the present invention, represented by the structural formula (229). d ] furan-6-amine (abbreviation: BBABnf(6)) is deposited to a thickness of 10 nm by vapor deposition to form a second hole transport layer 112-2; 2 on the hole transport layer (112-2), formula (x) which is 3,6-bis [4- (2-naphthyl) phenyl] -9 H-9-phenyl represented by - carbazole (abbreviation: βNP2PC) the The third hole transport layer 112-3 was formed by depositing to a thickness of 10 nm by evaporation.

Then, 7- [4- (10-phenyl-9-anthryl) phenyl] represented by the following structural formula (iv) -7 H - dibenzo [c, g] carbazole (abbreviation: cgDBCzPA) and formula (v) represented by N, N '- bis (3-methylphenyl) - N, N' - bis [4- (9-phenyl -9 H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (Abbreviation: 1,6mMemFLPAPrn) was co-deposited at a weight ratio of 1:0.03 (=cgDBCzPA: 1,6mMemFLPAPrn) to a thickness of 25 nm to form the light emitting layer 113.

Then, on the light emitting layer 113, cgDBCzPA was deposited to a thickness of 10 nm by evaporation, and vasophenanthroline (abbreviation: BPhen) represented by structural formula (vi) was deposited to a thickness of 15 nm by evaporation, thereby forming the electron transport layer 114 Formed.

After the electron transport layer 114 was formed, lithium fluoride (LiF) was deposited to a thickness of 1 nm by vapor deposition to form the electron injection layer 115. Then, the cathode 102 was formed by depositing aluminum to a thickness of 200 nm by evaporation. As a result, light-emitting element 4 of this example was fabricated.

(Method of manufacturing light-emitting element 5)

Light-emitting element 5, in place of the second hole transport layer (112-2) BBABnf (6) N , N -di (4-biphenyl) benzo[ b ]naphtho[1,2- d ]furan-8-amine It was formed in the same manner as Light-Emitting Element 4, except that it was formed using (abbreviation: BBABnf(8)).

The device structures of Light-Emitting Elements 4 and 5 are shown in the following table.

Light-emitting elements 4 and 5 were sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the atmosphere (specifically, a sealing material was applied to surround the element, and UV treatment and 80 1 hour of heat treatment at °C was performed). Then, the initial characteristics and reliability of this light-emitting device were measured. In addition, this measurement was carried out at room temperature (atmosphere maintained at 25°C).

42 shows the luminance-current density characteristics of Light-Emitting Elements 4 and 5. 43 shows current efficiency-luminance characteristics of Light-Emitting Elements 4 and 5. 44 shows luminance-voltage characteristics of Light-Emitting Elements 4 and 5. 45 shows current-voltage characteristics of Light-Emitting Elements 4 and 5. 46 shows external quantum efficiency-luminance characteristics of Light-Emitting Elements 4 and 5. 47 shows emission spectra of Light-Emitting Elements 4 and 5. Table 6 shows the main characteristics of Light-Emitting Elements 4 and 5 in the vicinity of 1000 cd/m ^2.

From FIGS. 42 to 46 and Table 6, it was found that the light emitting devices 4 and 5 of one embodiment of the present invention are blue light emitting devices having good efficiency and low driving voltage.

48 shows the driving time-dependent change of the luminance of the light emitting element under the condition that the current value is set to 2 mA and the current density is constant. As shown in FIG. 48, it was found that the light-emitting elements 4 and 5 maintain 85% or more of the initial luminance after 100 hours of driving, and are light-emitting devices having a very long life in which the decrease in luminance according to the driving time is very small.

(Example 8)

In this example, the light-emitting elements 6 and 7 of one embodiment of the present invention described in the first embodiment will be described. The structural formulas of the organic compounds used in Light-Emitting Elements 6 and 7 are shown below.

[Formula 71]

(Method of manufacturing light-emitting element 6)

First, on a glass substrate, a film of indium tin oxide (ITSO) containing silicon oxide was formed by sputtering to form an anode 101. The thickness was set to 70 nm, and the electrode area was set to 2 mm×2 mm.

Next, as a pretreatment for forming a light emitting device on the substrate, the surface of the substrate was washed with water and fired at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.

Thereafter, the ^{substrate was moved to a vacuum evaporation apparatus having a pressure reduced to about 10 -4} Pa, and vacuum firing was performed at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled for about 30 minutes. .

Next, the substrate provided with the anode 101 was fixed to the substrate holder provided in the vacuum evaporation apparatus so that the side on which the anode 101 was formed was facing downward. And, on the anode 101, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene represented by the structural formula (i) (abbreviation : HAT-CN) was deposited to a thickness of 5 nm by a deposition method using resistance heating to form a hole injection layer 111.

Next, on the hole injection layer 111, 4,4'-bis[ N- (1-naphthyl) -N -phenylamino]biphenyl (abbreviation: NPB) represented by the structural formula (ix) was deposited by evaporation. Depositing to a thickness of 20 nm to form the first hole transport layer 112-1; On the first hole transport layer 112-1, N , N -di(4-biphenyl)benzo[ b ]naphtho[1,2-, which is an organic compound of one embodiment of the present invention, represented by the structural formula (229). d ]furan-6-amine (abbreviation: BBABnf(6)) was deposited to a thickness of 10 nm by vapor deposition to form a second hole transport layer 112-2.

Then, 7- [4- (10-phenyl-9-anthryl) phenyl] represented by the following structural formula (iv) -7 H - dibenzo [c, g] carbazole (abbreviation: cgDBCzPA) and formula (v) represented by N, N '- bis (3-methylphenyl) - N, N' - bis [4- (9-phenyl -9 H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (Abbreviation: 1,6mMemFLPAPrn) was co-deposited at a weight ratio of 1:0.03 (=cgDBCzPA: 1,6mMemFLPAPrn) to a thickness of 25 nm to form the light emitting layer 113.

Then, on the light emitting layer 113, cgDBCzPA was deposited to a thickness of 10 nm by evaporation, and vasophenanthroline (abbreviation: BPhen) represented by structural formula (vi) was deposited to a thickness of 15 nm by evaporation, thereby forming the electron transport layer 114 Formed.

After the electron transport layer 114 was formed, lithium fluoride (LiF) was deposited to a thickness of 1 nm by vapor deposition to form the electron injection layer 115. Then, the cathode 102 was formed by depositing aluminum to a thickness of 200 nm by evaporation. As a result, light-emitting element 6 of this example was fabricated.

(Method of manufacturing light-emitting element 7)

Light-emitting element 7, in place of the second hole transport layer (112-2) BBABnf (6) N , N -di (4-biphenyl) benzo[ b ]naphtho[1,2- d ]furan-8-amine It was formed in the same manner as Light-Emitting Element 6, except that it was formed using (abbreviation: BBABnf(8)).

The device structures of Light-Emitting Elements 6 and 7 are shown in the following table.

Light-emitting elements 6 and 7 were sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the atmosphere (specifically, a sealing material was applied to surround the element, and UV treatment and 80 1 hour of heat treatment at °C was performed). Then, the initial characteristics and reliability of this light-emitting device were measured. In addition, this measurement was carried out at room temperature (atmosphere maintained at 25°C).

49 shows the luminance-current density characteristics of Light-Emitting Elements 6 and 7. 50 shows current efficiency-luminance characteristics of Light-Emitting Elements 6 and 7. 51 shows the luminance-voltage characteristics of Light-Emitting Elements 6 and 7. 52 shows current-voltage characteristics of Light-Emitting Elements 6 and 7. 53 shows external quantum efficiency-luminance characteristics of Light-Emitting Elements 6 and 7. 54 shows emission spectra of Light-Emitting Elements 6 and 7. Table 8 shows the main characteristics of Light-Emitting Elements 6 and 7 in the vicinity of 1000 cd/m ^2.

49 to 54 and Table 8, it was found that the light emitting devices 6 and 7 of one embodiment of the present invention are blue light emitting devices having good efficiency and low driving voltage.

(Example 9)

In this example, the light-emitting element 8 of one embodiment of the present invention described in the first embodiment will be described. The structural formula of the organic compound used in Light-Emitting Element 8 is shown below.

[Formula 72]

(Method of manufacturing light-emitting element 8)

First, on a glass substrate, a film of indium tin oxide (ITSO) containing silicon oxide was formed by sputtering to form an anode 101. The thickness was set to 70 nm, and the electrode area was set to 2 mm×2 mm.

Next, as a pretreatment for forming a light emitting device on the substrate, the surface of the substrate was washed with water and fired at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.

Thereafter, the ^{substrate was moved to a vacuum evaporation apparatus having a pressure reduced to about 10 -4} Pa, and vacuum firing was performed at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled for about 30 minutes. .

Next, the substrate provided with the anode 101 was fixed to the substrate holder provided in the vacuum evaporation apparatus so that the side on which the anode 101 was formed was facing downward. And, N , N -bis(biphenyl-4-yl)-6-phenylbenzo[ b ]naphtho[1,2- d ]furan-, which is an organic compound of one embodiment of the present invention represented by structural formula (146) 8-amine (abbreviation: BBABnf), and 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCNNQ) represented by structural formula (xi) by weight The hole injection layer 111 was formed by depositing to a thickness of 10 nm by co-deposition on the anode 101 in 2:1 (=BBABnf:F6-TCNNQ).

Next, BBABnf is deposited on the hole injection layer 111 to a thickness of 10 nm by evaporation, thereby forming the first hole transport layer 112-1, and 3-[4-(9-phenane) represented by structural formula (vii). to a thickness of 20nm by depositing by PCPPn) deposited on the first hole transport layer 112-1, a second hole transport layer (112-2) carbazole (abbreviated-trill) -phenyl] -9-phenyl-9-H Formed.

Then, 7- [4- (10-phenyl-9-anthryl) phenyl] represented by the following structural formula (iv) -7 H - dibenzo [c, g] carbazole (abbreviation: cgDBCzPA) and formula (v) represented by N, N '- bis (3-methylphenyl) - N, N' - bis [4- (9-phenyl -9 H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (Abbreviation: 1,6mMemFLPAPrn) was co-deposited at a weight ratio of 1:0.03 (=cgDBCzPA: 1,6mMemFLPAPrn) to a thickness of 25 nm to form the light emitting layer 113.

And, on the light-emitting layer 113, 2-[3'-(dibenzothiophen-4-yl)biphenyl-3-yl]dibenzo[ f , h ]quinoxaline (abbreviated name) represented by the structural formula (xii) : 2mDBTBPDBq-II) was deposited to a thickness of 10 nm by evaporation, and 2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline represented by structural formula (xiii) The electron transport layer 114 was formed by depositing (abbreviation: NBPhen) to a thickness of 15 nm by vapor deposition.

After the electron transport layer 114 was formed, lithium fluoride (LiF) was deposited to a thickness of 1 nm by vapor deposition to form the electron injection layer 115. Then, the cathode 102 was formed by depositing aluminum to a thickness of 200 nm by evaporation. Thereby, light-emitting element 8 of this example was fabricated.

The device structure of Light-Emitting Element 8 is shown in the table below.

Light-emitting element 8 was sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the atmosphere (specifically, a sealing material was applied to surround the element, and UV treatment and at 80°C during sealing. 1 hour of heat treatment was performed). Then, the initial characteristics and reliability of this light-emitting device were measured. In addition, this measurement was carried out at room temperature (atmosphere maintained at 25°C).

55 shows the luminance-current density characteristics of Light-Emitting Element 8. 56 shows current efficiency-luminance characteristics of Light-Emitting Element 8. 57 shows the luminance-voltage characteristics of Light-Emitting Element 8. 58 shows current-voltage characteristics of Light-Emitting Element 8. 59 shows external quantum efficiency-luminance characteristics of Light-Emitting Element 8. 60 shows an emission spectrum of Light-Emitting Element 8. Table 10 shows the main characteristics of Light-Emitting Element 8 in the vicinity of 1000 cd/m ^2.

55 to 60 and Table 10, it was found that the light emitting device 8 of one embodiment of the present invention is a blue light emitting device having good efficiency and low driving voltage.

Fig. 61 shows the driving time-dependent change of the luminance of the light emitting device under the condition that the current value is set to 2 mA and the current density is constant. As shown in FIG. 61, it was found that the light-emitting element 8 maintains 90% or more of the initial luminance after 100 hours of driving, and has a very small reduction in luminance according to the driving time, and has a long lifespan.

This application is based on the Japanese patent application of serial number 2016-016262 for which it applied to the Japan Patent Office on January 29, 2016, and the whole is incorporated by reference in this specification.

Reference Numerals 101: anode, 102: cathode, 103: EL layer, 111: hole injection layer, 112: hole transport layer, 112-1: first hole transport layer, 112-2: second hole transport layer, 112-3: third hole transport layer , 113: light emitting layer, 114: electron transport layer, 115: electron injection layer, 116: charge generation layer, 117: p-type layer, 118: electron relay layer, 119: electron injection buffer layer, 400: substrate, 401: anode, 403: EL Layer, 404: cathode, 405: sealing material, 406: sealing material, 407: sealing substrate, 412: pad, 420: IC chip, 501: anode, 502: cathode, 511: first light-emitting unit, 512: second light emission Unit, 513: charge generation layer, 601: driving circuit portion (source line driving circuit), 602: pixel portion, 603: driving circuit portion (gate line driving circuit), 604: sealing substrate, 605: sealing material, 607: space, 608 : Wiring, 609: flexible printed circuit (FPC), 610: device substrate, 611: switching FET, 612: current control FET, 613: anode, 614: insulator, 616: EL layer, 617: cathode, 618: light-emitting element, 730: insulating film, 770: planarizing insulating film, 772: conductive film, 782: light emitting element, 783: droplet ejection device, 784: droplet, 785: layer, 786: EL layer, 788: conductive film, 901: housing, 902: liquid crystal Layer, 903: backlight unit, 904: housing, 905: driver IC, 906: terminal, 951: substrate, 952: electrode, 953: insulating layer, 954: partition layer, 955: EL layer, 956: electrode, 1001: substrate , 1002: base insulating film, 1003: gate insulating film, 1006: gate electrode, 1007: gate electrode, 1008: gate electrode, 1020: first interlayer insulating film, 1021: second interlayer insulating film, 1022: electrode, 1024W: anode, 1024R: Anode, 1024G: anode, 1024B: anode, 1025: partition wall, 1028: EL layer, 10 Reference Numerals 29: cathode, 1031: sealing substrate, 1032: sealing material, 1033: transparent substrate, 1034R: red colored layer, 1034G: green colored layer, 1034B: blue colored layer, 1035: black matrix, 1036: overcoat layer, 1037: 3rd interlayer insulating film, 1040: pixel portion, 1041: driving circuit portion, 1042: peripheral portion, 1400: droplet ejection device, 1402: substrate, 1403: droplet ejection means, 1404: imaging means, 1405: head, 1406: dotted line, 1407: Control means, 1408: storage medium, 1409: image processing means, 1410: computer, 1411: marker, 1412: head, 1413: material source, 1414: material source, 1415: material source, 1416: head, 2001: housing, 2002 : Light source, 3001: lighting device, 5000: display area, 5001: display area, 5002: display area, 5003: display area, 5004: display area, 5005: display area, 7101: housing, 7103: display portion, 7105: stand, 7107: display, 7109: operation keys, 7110: remote controller, 7201: main body, 7202: housing, 7203: display, 7204: keyboard, 7205: external connection port, 7206: pointing device, 7210: second display, 7301: housing , 7302: housing, 7303: connection portion, 7304: display portion, 7305: display portion, 7306: speaker portion, 7307: recording medium insertion portion, 7308: LED lamp, 7309: operation key, 7310: connection terminal, 7311: sensor, 7401: Housing, 7402: display, 7403: control button, 7404: external connection port, 7405: speaker, 7406: microphone, 7400: mobile phone, 9033: clasp, 9034: switch, 9035: power switch, 9036: switch, 9038: Operation switch, 9310: portable information terminal, 9311: display panel, 9312: display area, 9313: hinge, 9315: housing, 9630: Housing, 9631: display, 9631a: display, 9631b: display, 9632a: touch screen area, 9632b: touch screen area, 9633: solar cell, 9634: charge/discharge control circuit, 9635: battery, 9636: DCDC converter, 9637: operation Key, 9638: converter, 9639: button

Claims (11)

As an organic compound represented by general formula (G1),

In General Formula (G1), R ¹ to R ⁸ are independently hydrogen, a C 1 to C 6 hydrocarbon group, a C 3 to C 6 cyclic hydrocarbon group, a C 1 to C 6 alkoxy group, a cyano group, a halogen, Represents any one of a haloalkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms,
One of A and B represents a group represented by the general formula (g3), and the other is hydrogen, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, halogen, and 1 to 6 carbon atoms. Represents any one of a haloalkyl group, a hydrocarbon group having 1 to 6 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms,

In general formula (g3), Ar ³ and Ar ⁴ are independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms, a substituted or unsubstituted benzonaphthofuranyl group, and a substituted or unsubstituted dynapthofuran Represents any one of the diaries, Ar ⁵ and Ar ⁶ independently represent a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 54 carbon atoms, n and m independently represent 0 to 2, Ar ³ and Ar ⁵ The sum of carbon number of is 60 or less, and the sum of carbon number of Ar ⁴ and Ar ⁶ is 60 or less. The method of claim 1,
Ar ³ and Ar ⁴ independently represent any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, and a substituted or unsubstituted pyrenyl group. . The method of claim 1,
The Ar ⁵ and Ar ⁶ are independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, and a substituted or unsubstituted pyrenylene group. Representing, organic compounds. The method of claim 1,
Each of Ar ³ and Ar ⁴ is a phenyl group, an organic compound. The method of claim 1,
Each of the Ar ⁵ and Ar ⁶ is a phenylene group, an organic compound. The method of claim 1,
One of the n and m is 1 and the other is 0, an organic compound. The method of claim 1,
Wherein A is a phenyl group, an organic compound. The method of claim 1,
The HOMO level of the organic compound is -5.4 eV or more, an organic compound. As a light emitting element,
anode;
cathode; And
Including an EL layer,
The EL layer includes a light emitting layer,
The EL layer is located between the anode and the cathode,
The light-emitting device, wherein the EL layer contains the organic compound according to claim 1. The method of claim 9,
The light-emitting layer includes a light-emitting material and the organic compound. The method of claim 10,
The light-emitting layer further includes an electron transport material.

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